KR100838142B1 - Antireflection film, polarizing plate and image display device - Google Patents

Abstract

The present invention can provide an antireflection film improved in the scratch resistance while having a sufficiently high antireflection property, and a polarizing plate and a display device using the antireflection film. The antireflection film comprises a transparent support, and as an outermost layer, a low refractive index layer containing a fluorine-containing polymer. The low refractive index layer comprises at least one inorganic fine particle having an average particle size of 30 to 100% of the thickness of the low refractive index layer. The inorganic particle is a silica fine particle, and at least one of the silica fine particles in the low refractive index layer is a hollow silica fine particle having a refractive index of from 1.17 to 1.40. Moreover, the hollow silica fine particle comprises an outer shell and a single vacancy inside the particle, and a porosity of the hollow silica fine particle defined by formula (VIII) is from 10 to 60%: x = 4 ¢ À ¢ a 3 / 3 / 4 ¢ À ¢ b 3 / 3 × 100 wherein a is a radius of the vacancy and b is the radius of the outer shell.

Description

Anti-reflection film, polarizer and video display device {ANTIREFLECTION FILM, POLARIZING PLATE AND IMAGE DISPLAY DEVICE}

The present invention relates to an antireflection film and a polarizing plate and an image display device using the antireflection film.

In display devices such as cathode ray tube display devices (CRTs), plasma display panels (PDPs), electroluminescent displays (ELDs) and liquid crystal display devices (LCDs), anti-radiation films are generally disposed on the outermost surface of the display, This reduces the contrast caused by the reflection of external light or prevents the entry of the image by the reflection.

Generally, the antireflective film is prepared by forming a low refractive index layer on the support to an appropriate thickness, where the refractive index of the low refractive index layer is lower than the refractive index of the support. In order to realize low reflectance, a material with the lowest refractive index is preferably used for the low refractive index layer. In addition, antireflective films are used on the outermost surface of the display, and therefore, the films are required to have high scratch resistance. In order to realize the high scratch resistance of thin films with a thickness of about 100 nm, the strength of the film itself and a tight attachment to the lower layer is required.

In order to lower the refractive index of the material, (1) introduction of fluorine atoms and (2) reduction of density (introduction of voids) can be used, but in all of the above techniques, the adhesion property in the film strength or gap is reduced. And tend to result in low scratch resistance. Therefore, it was difficult to realize low refractive index and high scratch resistance at the same time.

   As described in JP-A-2002-265866 (the term "JP-A" as used herein means "unexamined Japanese Patent Application") and JP-A-2002-317152, the film strength is: Although it may be increased to some extent by the method using a fluorine-containing sol-gel film, the method, for example, (1) curing requires heating over a long period of time, the load of production is large or (2) the film There is no resistance to silver saponification solution (alkali treatment solution), and in the case of saponification of TAC surface, this treatment causes a large constraint, which cannot be performed after the anti-radiation film is formed.

On the other hand, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709 introduce a polysiloxane structure into the fluorine-containing polymer, thereby reducing the coefficient of friction of the film surface, thereby improving scratch resistance. Describe techniques to improve. The technique is somewhat effective for improving scratch resistance, but for films lacking substantial film strength and gap adhesion, sufficiently high scratch resistance cannot be achieved solely by the technique.

An object of the present invention is to provide an antireflection film having improved scratch resistance while maintaining sufficiently high antireflection characteristics. An object of the present invention includes providing a polarizing plate and a display device using the antireflection film.

As a result of extensive investigations, the inventors have found that when one or more inorganic particles having a particle size corresponding to the thickness of a low refractive index layer comprising a fluorine-containing polymer are used in the low refractive index layer, the film strength is significantly improved, It has been found that the increase in the refractive index of itself can be suppressed, which is also not subject to long term thermal curing or saponification treatment.

According to the present invention, an antireflection film, a polarizing plate and a display device having the following structure are provided, whereby the object described above is achieved.

1.Anti-reflection film comprising:

Transparent support; And a low refractive index layer comprising a fluorine-containing polymer as the outermost layer

(The low refractive index layer comprises one or more inorganic fine particles having an average particle size of 30 to 100% of the low refractive index layer thickness).

2. The antireflective film of item 1, having one or more hard coat layers between the transparent support and the low refractive index layer.

3. The antireflection film according to item 1 or 2, wherein the inorganic particles are silica fine particles.

4. The antireflection film according to any one of items 1 to 3, wherein the low refractive index layer further comprises one or more silica fine particles having a particle size of less than 25% of the thickness of the low refractive index layer.

5. The antireflective film of item 3 or 4, wherein the one or more silica fine particles of the low refractive index layer are hollow silica fine particles having a refractive index of 1.17 to 1.40.

6. The fluorine-containing polymer according to any one of items 1 to 5, wherein the fluorine-containing polymer is a copolymer (P) having a main chain consisting solely of carbon atoms, the copolymer comprising: a fluorine-containing vinyl monomer polymerization unit; And a polymerization unit having a (meth) acryloyl group in the side chain.

7. The antireflection film according to item 6, wherein the copolymer (P) is represented by the following general formula (1):

[Wherein L represents a linking group having 1 to 10 carbon atoms, m represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents an arbitrary vinyl monomer polymerization unit and a single component or a plurality of components Wherein x, y and z represent mole percent of each component and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70 and O ≦ z ≦ 65.

8. The method according to any of items 2 to 7, wherein at least one hard coating layer is a light-diffusion layer, the light-diffusion layer having an exit angle of 0 ° in the scattered light profile by a goniophotometer ( antireflection film having a scattering luminous intensity of 30 ° from 0.01 to 0.2% relative to luminous intensity at exit angle).

9. The method of any one of items 1 to 8, comprising at least one high refractive index layer between the transparent support and the low refractive index layer, wherein the high refractive index layer has a refractive index of 1.55 to 2.40 and comprises titanium dioxide; And an inorganic fine particle comprising at least one element selected from cobalt, aluminum and zirconium.

10. The antireflection film according to any one of items 1 to 9, wherein the low refractive index layer has a refractive index of 1.20 to 1.49.

11. A polarizing plate comprising two protective films of a polarizer and a polarizer, wherein one of the two protective films of the polarizer is the antireflective film described in any one of items 1 to 10.

12. The polarizing plate according to item 11, wherein the non-reflective film of the two protective films of the polarizer is an optical correction film having an optical correction layer comprising an optically anisotropic layer,

The optically anisotropic layer is a layer having a negative birefringence, comprising a compound having a discotic structural unit, the disc plane of the discotic structural unit is inclined with respect to the surface protective film plane, the discotic structural unit The angle created by the disk plane and the surface protective film plane of the polarizing plate changes in the depth direction of the optically anisotropic layer.

13. An image display device comprising the antireflection film described in any one of items 1 to 10 or the polarizing plate described in item 11 or item 12 as the outermost surface of the display.

14. A TN-, STN-, VA-, IPS- or OCB-type transmissive, reflective or transflective type liquid crystal display device comprising one or more polarizers described in item 11 or item 12.

1 (a) and (b) are schematic cross-sectional views showing the layer structure of the antiglare and antireflective film.

Description of Numeric Quotation

1 antireflection film

2 transparent support antireflection layer

4 glare resistant hard coating layer

5 low refractive index layer

6 mat particles

7 refractive index layer

8 high refractive index layer

BEST MODE FOR CARRYING OUT THE INVENTION

The basic structure of the antireflection film according to the preferred embodiment of the present invention is described below with reference to the drawings.

Figure 1 (a) is a cross-sectional view schematically showing one embodiment of the antireflective film of the present invention. The antireflection film 1 has a layer structure in the order of the transparent support 2, the hard coating layer 3, the antiglare hard coating layer 4 and the low refractive index layer 5. The matte particles 6 are dispersed in the antiglare hard coat layer 4, and the material constituting the portion other than the matte particles 6 of the antiglare hard coat layer 4 preferably has a refractive index of 1.50 to 2.00. Have The refractive index of the low refractive index layer 5 is preferably 1.35 to 1.49. In the present invention, the hard coat layer may or may not have the above antiglare properties and may consist of one layer or a plurality of layers, for example two, three or four layers. In addition, the hard coat layer may not be coated. Thus, although the hard coat layer 3 and the antiglare hard coat 4 shown in FIG. 1 are not essential, in order to impart film strength, one of the hard coat layers is preferably provided. The low refractive index layer serves as the outermost layer.

1 (b) is a cross-sectional view schematically showing one embodiment of the antireflective film of the present invention, wherein the antireflective film 1 is a transparent support 2, a hard coating layer 3, a medium refractive index layer 7 ), High refractive index layer 8 and low refractive index layer 5 (outermost layer) in this order. The transparent support 2, the medium refractive index layer 7, the high refractive index layer 8 and the low refractive index layer 5 have a refractive index satisfying the following relationship:

(Refractive index of high refractive index layer)> (Refractive index of medium refractive index layer)> (Refractive index of transparent support)> (Refractive index of low refractive index layer)

As described in JP-A-59-50401, in the layer structure shown in Fig. 1 (b), the medium refractive index layer, the high refractive index layer and the low refractive index layer are preferably represented by the following formulas I, II and III, respectively. Satisfies:

[Wherein h represents a positive integer (generally 1, 2 or 3), n ₁ represents the refractive index of the medium refractive index layer, d ₁ represents the layer thickness (nm) of the medium refractive index layer, and λ is Represents the wavelength of visible light (nm) and is a value between 380 and 680 nm;

[Wherein i represents a positive integer (generally 1, 2 or 3), n ₂ represents the refractive index of the high refractive index layer, d ₂ represents the layer thickness (nm) of the high refractive index layer, and λ is Represents the wavelength of visible light in nm and is in the range of 380-680 nm;

[Wherein j represents a positive odd number (generally 1), n ₃ represents the refractive index of the low refractive index layer, d ₃ represents the layer thickness (nm) of the low refractive index layer, and λ represents the wavelength of visible light ( nm) and a value between 380 and 680 nm.

In the layer structure shown in Fig. 1 (b), the medium refractive index layer, the high refractive index layer and the low refractive index layer preferably satisfy the following formulas IV, V and VI, respectively:

[Wherein λ is 500 nm, h is 1, i is 2 and j is 1].

High refractive index, medium refractive index and low refractive index as used herein mean the relative height of the refractive index between the layers. In Fig. 1 (b), a high refractive index is used as the optical interference layer, and thus an antireflective film having a remarkably good antireflection performance can be produced.

[Low refractive index layer]

Low refractive index layers for use in the present invention are described below.

The low refractive index layer of the antireflective film of the present invention has a refractive index of 1.20 to 1.49, preferably 1.30 to 1.44.

In addition, in view of obtaining low reflectance, the low refractive index layer preferably satisfies the following formula (VII):

[Wherein m represents a positive odd number, n ₁ represents the refractive index of the low refractive index layer, d ₁ represents the layer thickness (nm) of the low refractive index layer, and λ represents the wavelength and is in the range of 500 intrinsic 550 nm. Value].

If Equation VII is satisfied, this means that m (positive odd number, generally 1) satisfying Equation VII exists in the above-described wavelength range.

The constituent materials for forming the low refractive index layer of the present invention are described below.

The low refractive index layer of the present invention comprises a fluorine-containing polymer as the low refractive index binder. The fluoropolymer is preferably a fluorine-containing polymer having a dynamic coefficient of friction of 0.03 to 0.15 and a contact angle of water of 90 to 120 ° and capable of crosslinking by heat or ionizing radiation. In the low refractive index layer of the present invention, inorganic fillers may also be used to improve film strength.

Examples of fluorine-containing polymers for use in the low refractive index layer include valences of perfluoroalkyl group-containing silane compounds (eg, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) Decomposition products and dehydration-condensates, and fluorine-containing copolymers using constituent units for imparting crosslinking reactivity with fluorine-containing monomer units.

Specific examples of the fluorine-containing monomer units include fluoroolefen (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2 -Dimethyl-1,3-dioxol), partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (e.g., BISCOTE 6FM (manufactured by Osaka Yuki Kagaku), M-2020 (manufactured by Daikin Corporation)) , And fully or partially fluorinated vinyl ethers. Among them, perfluoroolefins are preferred, and hexafluoropropylene is more preferable in view of refractive index, solubility, transparency and easy availability.

Examples of structural units for imparting crosslinking reactivity include structural units obtained by a polymerization reaction of monomers such as glycidyl (meth) acrylate and glycidyl vinyl ether which already have a self-crosslinking functional group in the molecule; Monomers having carboxyl, hydroxy, amino or sulfo groups, such as (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether Structural units obtained by the polymerization reaction of millelic acid and crotonic acid; And after the crosslinking reactive group such as (meth) acryloyl group has been introduced into the structural unit described above by the polymer reaction (the crosslinking reactive group can be introduced, for example, by allowing the acrylic acid to act as a hydroxy group). Contains structural units.

In consideration of solubility in the solvent, transparency of the film, and the like, in addition to the fluorine-containing monomer unit and the structural unit for imparting crosslinking reactivity, monomers containing no fluorine atom may also be appropriately copolymerized. The monomer units that can be used in combination are not particularly limited, examples of which include olefins (eg ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg methyl acrylate, methyl acrylate) , Ethyl acrylate, 2-ethylhexyl acrylate), methacrylic acid esters (e.g. methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene derivatives (e.g. For example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ethers (e.g. methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether), vinyl esters (e.g. vinyl acetate, vinyl pro Cypionate, vinyl cinnamate), acrylamide (eg N-tert-butylacrylamide, N-cyclohexylacrylamide) And a nitrile derivative with acrylamide and acrylic.

As described in JP-A-10-25388 and JP-A-10-147739, with the polymers, a curing agent may be used as appropriate.

Particularly useful fluorine-containing polymers in the present invention are random copolymers of perfluoroolefins and vinyl ethers or esters. In particular, the fluorine-containing polymer preferably has groups capable of crosslinking reaction alone (for example, radical reactive groups such as (meth) acryloyl groups, or ring-opening polymerizable groups such as epoxy groups and oxetanyl groups). . The crosslinking reactive group containing the polymerized unit preferably accounts for 5 to 70 mol%, more preferably 30 to 60 mol% of the total polymerized units of the polymer.

A preferred embodiment of the copolymer for use in the present invention is a copolymer represented by the formula (1).

In Formula 1, L may have a linear, branched or cyclic structure, and may have a hetero atom selected from O, N or S, 1 to 10 carbon atoms, preferably 1 to 6, more preferably 2 And a linking group having 4 to 4.

Preferred examples thereof are *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O-**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, * -CONH- (CH ₂ ) ₃ -O-**, * -CH ₂ CH (OH) CH ₂ -O-** and * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* denotes the binding site in the polymer backbone, ** denotes the binding site of the (meth) acryloyl group moiety. It represents). m represents 0 or 1.

In the formula (1), X represents a hydrogen atom or a methyl group, and in view of curing reactivity, preferably represents a hydrogen atom.

In formula (1), A represents a repeating unit derived from any vinyl monomer, which is not particularly limited as long as it is a monomer component copolymerizable with hexafluoropropylene. The repeating unit may be appropriately selected in consideration of various aspects such as adhesion to a substrate, Tg of the polymer (which contributes to film firmness), solubility in solvents, transparency, slippage, and dust / soil protection properties, and It can therefore consist of a single vinyl monomer or a plurality of vinyl monomers.

Preferred examples thereof include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyether vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether and Allyl vinyl ethers; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (Meth) acrylates such as ethyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyl Oxypropyltrimethoxysilane; Styrene derivatives such as styrene and p-hydroxymethylstyrene; Unsaturated carboxylic acids such as crotonic acid, maleic acid and itaconic acid; And derivatives thereof. Among them, more preferred are vinyl ether derivatives and vinyl ester derivatives, and more preferred are vinyl ether derivatives.

x, y and z represent the mole percentages of the respective constituents, and 30 ≦ x ≦ 60, 5 ≦ y ≦ 70 and O ≦ z ≦ 65, preferably 35 ≦ x ≦ 55, 30 ≦ y ≦ 60 and O ≤ z ≤ 20, more preferably 40 ≤ x ≤ 55, 40 ≤ y ≤ 55 and O ≤ z ≤ 10.

A more preferred embodiment of the copolymer for use in the present invention is a copolymer represented by the following formula (2).

In formula (2), X, x and y have the same meaning as in formula (1), and their preferred ranges are also the same.

n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, more preferably 2 ≦ n ≦ 4.

B represents a repeating unit derived from any vinyl monomer and may consist of a single composition or a plurality of compositions. Examples thereof include those described above as examples of A in formula (1).

z1 and z2 represent the mole percent of each repeating unit, and O≤zl≤65 and O≤z2≤65, preferably O≤zl≤30 and O≤z2≤10, more preferably 0≤z1≤10 And a value satisfying O ≦ z 2 ≦ 5.

The copolymer represented by the formula (1) or (2) is, for example, according to one of the above-described methods, a (meth) acryloyl group as a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component By introducing.

Preferred examples of copolymers useful in the present invention are as shown below, but are not limited to the present invention.

* Indicates a polymer backbone portion and ** indicates a (meth) acryloyl group portion.

* Indicates a polymer backbone portion and ** indicates a (meth) acryloyl group portion.

* Indicates a polymer backbone portion and ** indicates a (meth) acryloyl group portion.

Copolymers for use in the present invention are synthesized precursors such as hydroxyl group-containing polymers according to various types of polymerization methods such as solution polymerization method, precipitation polymerization method, suspension polymerization method, bulk polymerization method and emulsion polymerization method , By introducing (meth) acryloyl groups via the polymer reactions described above. The polymerization reaction can be carried out by known processes such as batch systems, semicontinuous systems and continuous systems.

For the initiation of the polymerization reaction, for example, a method using a radical initiator and a method of irradiation or radiation can be used. The polymerization method and the polymerization reaction initiation method are described, for example, in Teiji Tsuruta, Kobunshi Gosei Hoho (Polymer Synthesis Method) , revised edition, Nikkan Kogyo Shinbun Sha (1971), and Takayuki Ohtsu and Masaetsu Kinoshita, Kobunshi Goseino. Jikken Ho (Experimentation Methods of Polymer Synthesis) , pp. 124-154, Kagaku Dojin (1972).

Of the above polymerization methods, a solution polymerization method using a radical initiator is preferable. Examples of solvents for use in solution polymerization reactions include various organic solvents, such as ether ether, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylform Amides, N, N-dimethylacetamide, benzene, toluene, acetonitrile, methyl chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol. The solvents may be used individually or as a combination of two or more thereof, or may be used as a solvent mixed with water.

The polymerization temperature needs to be set according to the molecular weight of the polymer to be produced, the type of initiator, and the like, and may be 0 ° C. or less or 100 ° C. or more, but the polymerization reaction is preferably performed at a temperature of 50 to 100 ° C.

The reaction pressure may be appropriately selected but is usually on the order of 1 to 100 kg / cm 2, preferably 1 to 30 kg / cm 2. The reaction time is approximately 5 to 30 hours.

Reprecipitation solvents for the polymers obtained are preferably isopropanol, hexane, methane and the like.

In the present invention, the low refractive index layer comprises one or more inorganic fine particles. The inorganic fine particles are described below.

The amount of inorganic fine particles to be coated is preferably 1 to 100 mg / m 2, more preferably 5 to 80 mg / m 2, particularly more preferably 10 to 60 mg / m 2. If the amount to be coated is too small, the effect of improving scratch resistance is reduced, while in the case of excessively large amounts, fine aspersities are formed on the surface of the low refractive index layer, which is black non-loosening. Or deteriorates appearance, such as integrated reflectance.

The inorganic fine particles are included in the low refractive index layer, so the particles preferably have a low refractive index. Examples of the particles include fine particles of magnesium fluoride or silica. In particular, silica fine particles are preferred in consideration of refractive index, dispersion stability and price. The average particle size of the silica fine particles is preferably 30 to 100%, more preferably 35 to 80%, particularly more preferably 40 to 60% of the thickness of the low refractive index. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 to 100 nm, more preferably 35 to 80 nm, particularly more preferably 40 to 60 nm.

If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced, while if it is excessively large, fine aspersities are formed on the surface of the low refractive index layer, which leads to black unresolved ( Deteriorates appearance, such as non-loosening or integrated reflectance. The silica fine particles may be crystalline or amorphous, may be monodisperse particles, or may be aggregated particles as long as a predetermined particle size is satisfied. The form is most preferably spherical, but no problem occurs even if it is amorphous. The above descriptions relating to silica fine particles also apply to other inorganic particles.

Average particle size of inorganic fine particles is measured by Coulter Calculator.

In order to further reduce the increase in the refractive index of the low refractive index layer, hollow silica fine particles are preferably used. The refractive index of the hollow silica fine particles is 1.17 to 1.40, preferably 1.17 to 1.35, more preferably 1.17 to 1.30. Although the refractive index used here shows the refractive index of the whole particle | grain, it does not show the refractive index only of the silica as an outer shell which forms hollow silica particle. Here, assuming that the radius of the inner space of the particle is a and the radius of the outer shell of the particle is b, the porosity x represented by the following formula VIII is preferably 10 to 60%, more preferably 20 to 60 %, Most preferably 30 to 60%:

If the hollow silica particles have a further reduced index of refraction and increased porosity, the thickness of the outer shell becomes smaller and the strength of the particles decreases. Therefore, in view of scratch resistance, particles having a low refractive index of less than 1.17 are suitable.

The refractive index of the hollow silica particles is measured by Abbe's refractometer (manufactured by ATAGO K.K.).

In addition, one or more silica fine particles having an average particle size of less than 25% of the low refractive index layer (such fine particles are referred to as " small particle size silica fine particles ") are preferably silica having the particle sizes described above. Fine particles (such fine particles are referred to as " large particle size silica fine particles ") and used.

The small particle sized silica fine particles may be present in the space between the large particle sized silica fine particles, and thus may serve as a holding agent for the large particle sized silica fine particles.

At low refractive index layer thicknesses of 100 nm, the average particle size of the small particle size silica fine particles is preferably 1 to 20 nm, more preferably 5 to 15 nm, particularly more preferably 10 to 15 nm. In view of the raw material retainer effect, the use of the silica fine particles is preferred.

Silica fine particles are subjected to physical surface treatments such as plasma discharge treatment and corona discharge treatment, or chemical surface treatment with surfactants, coupling agents, etc., to stabilize dispersion in dispersion or coating solutions, or affinity for binder components. Or to enhance its binding properties. Particular preference is given to the use of coupling agents. As the coupling agent, an alkoxy metal compound (for example, titanium coupling agent, silane coupling agent) is preferably used. In particular, the treatment with a silane coupling agent is effective.

The coupling agent is used as a surface treatment agent for applying the surface treatment to the inorganic filler of the low refractive index layer in advance before the coating solution of the low refractive index layer is prepared, but the coupling agent is preferably a It is further added as additive in the preparation and introduced into the layer.

The silica fine particles are preferably dispersed in the medium without surface treatment, reducing the load of the surface treatment.

In view of scratch resistance, the at least one hard coating layer and at least one layer of the low refractive index layer constituting the antireflective film of the present invention are preferably organosilane compounds and / or hydrolysates thereof and / or partial condensates thereof, The so-called sol component (as referred to below) is included in the coating solution forming the layer. In particular, in order to achieve both antireflection performance and scratch resistance, the low refractive index layer preferably comprises an organosilane compound, its hydrolyzate and / or partial condensate, and the hard coating layer preferably comprises an organosilane compound, Hydrolysates and / or partial condensates thereof, or mixtures thereof. The sol component condenses to form a cured product upon drying and heating of the coating solution after coating and becomes a binder of the layer. When the cured product has a polymerizable saturated bond, a binder having a tertiary structure is formed upon irradiation of actinic light.

The organosilane compound is preferably represented by the following formula (3):

In formula (3), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, hexyl, decyl and hexadecyl. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and even more preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X represents a hydrolyzable group. Examples of such groups include alkoxy groups (preferably alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups), halogens (such as Cl, Br and I) and groups represented by R ² COO (R ² is preferably Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO and C ₂ H ₅ COO. Especially, an alkoxy group is preferable and a methoxy group and an ethoxy group are more preferable.

m represents an integer of 1 to 3, preferably 1 or 2, more preferably 1.

When a plurality of R ¹⁰ or X are present, the plurality of R ¹⁰ or X may be the same or different.

Substituents included in R ¹⁰ are not particularly limited, but examples thereof include halogen (eg fluorine, chlorine, bromine), hydroxyl group, metcapto group, carboxyl group, epoxy group, alkyl group (eg methyl , Ethyl, i-propyl, propyl, tert-butyl), aryl groups (e.g. phenyl, naphthyl), aromatic heterocyclic groups (e.g. furyl, pyrazolyl, pyridyl), alkoxy groups (e.g. , Methoxy, ethoxy, i-propoxy, hexyloxy), aryloxy group (e.g. phenoxy), alkylthio group (e.g. methylthio, ethylthio), arylthio group (e.g. For example, phenylthio), alkenyl groups (e.g., vinyl, 1-propenyl), acyloxy groups (e.g., acetoxy, alyloyloxy, methacryloyloxy), alkoxycarbonyl groups (e.g. , Methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (e.g. phenoxycarbonyl), carbamoyl group (e.g. carbamoyl, N-methylca Rivamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl) and acylamino groups (eg, acetylamino, benzoylamino, acylamino, methacrylamino groups). Each of the above substituents may be further substituted.

When a plurality of R ^{10 's} are present, at least one is preferably a substituted alkyl group or a substituted aryl group. In particular, organosilane compounds having a vinyl polymerizable substituent represented by the following general formula (4) are preferred:

In formula (4), R ¹ represents hydrogen, methyl group, methoxy group, alkoxycarbonyl group, cyano group, fluorine or chlorine. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ¹ preferably denotes hydrogen, methyl group, methoxy group, methoxycarbonyl group, cyano group, fluorine or chlorine, more preferably hydrogen, methyl group, methoxycarbonyl group, fluorine or chlorine, particularly more preferably or methyl group.

Y is a single bond, * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, more preferably Single bond or * -COO-**, and most preferably * -COO-**. * Denotes the position bonded to = C (R ¹ )-and ** denotes the position bonded to L.

L represents a divalent linking chain. Embodiments thereof include substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted alkylene groups having a linking group therein (eg, ether, ester, amido), and It includes a substituted or unsubstituted arylene group having a linking group therein. L is preferably an alkylene group having a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group or a linking group therein, more preferably an unsubstituted alkylene group, an unsubstituted arylene group or an ether therein. Or an alkylene group having an ester linking group, more preferably an unsubstituted alkylene group or an alkylene group having an ether or ester linking group therein. Examples of the substituent include halogen, hydroxyl group, mercapto group, carboxyl group, epoxy group, alkoxy group and aryl group. Each of the unsubstituted groups may be further substituted.

 n is 0 or 1; When a plurality of X's are present, the plurality of X's are the same or different. n is preferably 0.

R ¹⁰ has the same meaning as in Formula 3, and preferably represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, more preferably an unsubstituted alkyl group or an unsubstituted aryl group.

X has the same meaning as in formula (3), preferably halogen, hydroxyl group or unsubstituted alkoxy group, more preferably chlorine, hydroxyl group or unsubstituted alkoxy group having 1 to 6 carbon atoms, particularly more preferably Preferably a hydroxyl group or an alkoxy having 1 to 3 carbon atoms, and particularly preferably a methoxy group.

The compounds represented by the formulas (3) and (4) can be used as a combination of two or more thereof. Specific examples of the compounds represented by the formulas (3) and (4) are shown below, but the present invention is not limited thereto.

Especially, (M-1), (M-2), and (M-5) are preferable.

Hydrolysates and / or partial condensates of organosilane compounds for use in the present invention are described in more detail below.

The hydrolysis and / or condensation reaction of the organosilane is generally carried out in the presence of a catalyst. Examples of catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; Organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; Organic bases such as triethylamine and pyridine; Metal alkoxides such as triisopropylaluminum and tetrabutoxyzirconium; And metal chelate compounds wherein the central metal is a metal such as Zr, Ti or Al. Among inorganic acids, hydrochloric acid and sulfuric acid are preferable, and among organic acids, it is preferable to have an acid dissociation constant (pKa value (25 degreeC)) of 4.5 or less in water. Organic acids having acid dissociation constants of 3.0 or less in hydrochloric acid, sulfuric acid and water are more preferred, organic acids having acid dissociation constants of 2.5 or less in hydrochloric acid, sulfuric acid and water are particularly preferred, and acid dissociation constants of 2.5 or less in water Branches are more preferably organic acids, methanesulfonic acid, oxalic acid, phthalic acid and malonic acid are particularly preferred, and oxalic acid is particularly preferred.

The hydrolysis / condensation reaction of the organosilane can be carried out in a solvent-free system or in a solvent, but an organic solvent is preferably used for uniformly mixing the components. Suitable examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones and esters.

Preference is given to solvents capable of decomposing organosilanes and catalysts. The use of an organic solvent as a coating solution or as part of a coating solution is preferred in view of the process, and solvents which do not impair solubility and dispersibility when mixed with other constituent materials such as fluorine-containing polymers are preferred.

Examples of alcohols include monohydric alcohols and dihydric alcohols. The monohydric alcohol is preferably a saturated aliphatic alcohol having 1 to 8 carbon atoms. Specific examples of the alcohol include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol mono Butyl ether and ethylene acetate glycol monoethyl ether.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. Specific examples of ethers include ethyl acetate, propyl acetate, butyl acetate and propylene carbonate.

One of the organic solvents may be used alone, or two or more thereof may be used as a combination. The solid content concentration during the reaction is not particularly limited, but it is usually 1 to 90%, preferably 20 to 70%.

Water is added in an amount of 0.3 to 2 moles, preferably 0.5 to 1 mole, per mole of hydrolyzable groups of the organosilane, and the resulting solution is 25 to 100 in the presence of the solvents described above and in the absence of a catalyst. The reaction is carried out by stirring at < RTI ID = 0.0 >

In the present invention, hydrolysis is an alcohol represented by the formula R ³ OH (R ³ represents an alkyl group having 1 to 10 carbon atoms) and a compound represented by the formula R ⁴ COCH ₂ COR ⁵ (R ⁴ is a 1 to 10 carbon atoms An alkyl group, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) is present as a ligand and the central metal is a metal selected from Zr, Ti and Al in the presence of at least one metal chelate compound It is preferably carried out by stirring the solution at 25 to 100 ° C.

The metal chelate compound is not particularly limited, and an alcohol represented by the formula R ³ OH (R ³ represents an alkyl group having 1 to 10 carbon atoms) and a compound represented by the formula R ⁴ COCH ₂ COR ⁵ (R ⁴ represents 1 to Any compound so long as it represents an alkyl group of 10, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) as a ligand and the central metal is a metal chelate compound selected from Zr, Ti and Al This can be used as appropriate. Metal chelate compounds for use in the present invention are preferably of the formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 and Al (OR ³ ) _r1 ( R ⁴ COCHCOR ⁵ ) _{r 2} , wherein the compound has the activity of accelerating the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

In the metal chelate compound, R ³ and R ⁴ may be the same or different, and each of an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, a phenyl group, etc. are shown. R ⁵ is the same as an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec- Butoxy group and tert- butoxy group are shown. Further, in the metal chelate compound, p1, p2, q1, q2, r1 a and r2 each represent an integer determined to satisfy the relationship of p1 + p2 = 4, q1 + q2 = 4 and r1 + r2 = 3.

Specific examples of the metal chelate compounds include zigconium chelate compounds such as zigconium tri-n-butoxyethylacetoacetate, zigconium di-n-butoxy-bis (ethylacetoacetate), zigconium n-butoxy-tris ( Ethyl acetoacetate), zigconium tetrakis (n-propylacetoacetate), zigconium tetrakis (acetylacetoacetate) and zigconium tetrakis (ethylacetoacetate); Titanium chelate compounds such as titanium diisopropoxy-bis (ethylacetoacetate), titanium diisopropoxybis (acetylacetate) and titanium diisopropoxy-bis (acetylacetone); And aluminum chelate compounds such as aluminum diisopropoxyethylacetoacetate, aluminum diisopropoxyacetylacetonate, aluminum isopropoxy-bis (ethylacetoacetate), aluminum isopropoxy-bis (acetylacetonate), aluminum tris (Ethylacetoacetate), aluminum tris (ethylacetonate), aluminum tris (acetylacetonate) and aluminum monoacetylacetonato-bis (ethylacetoacetate).

Among the metal chelate compounds, preferred are zigconium tri-n-butoxyethylacetoacetate, titanium diisopropoxy-bis (acetylacetonate), aluminum diisopropoxyethylacetoacetate and aluminum tris (ethylacetoacetate). to be. The metal chelate compounds may be used individually or as mixtures of two or more thereof. Partial hydrolysates of such metal chelate compounds may also be used.

The metal chelate compound is used in an amount of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass relative to the organosilane compound. When the amount is added below 0.01% by mass, the condensation reaction of the organosilane compound proceeds slowly, and the coating film may deteriorate in durability, while when the amount exceeds 50% by mass, Compositions comprising hydrolysates and / or partial condensates may be degraded in storage stability, which is therefore undesirable.

In the coating solution for forming the hard coating layer or the low refractive index layer used in the present invention, the β-diketone compound and / or the β-ketone ester compound may be a hydrolyzate and / or part of a metal chelate compound and an organosilane compound. In addition to the composition comprising the condensate, it is preferably added. This is further described below.

Compounds for use in the present invention are β-diketone compounds and / or β-ketone ester compounds represented by the formula R ⁴ COCH ₂ COR ⁵ , which compounds have activity as stability enhancers for the compositions used in the present invention. . That is, the compound is considered to be coordinated with a metal atom in the metal chelate compound (zigconium, titanium and / or aluminum compound), and the metal chelate compound accelerates the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound. Suppressing the activity, thereby improving the storage stability of the composition thus obtained. R ⁴ and R ⁵ constituting the β-diketone compound and the β-ketoester compound have the same meanings as R ⁴ and R ⁵ constituting the metal chelate compound.

 Specific examples of the β-diketone compound and / or the β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl aceto Acetate, tert-butyl acetoacetate, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione and 5- Methyl-hexane-dione. Especially, ethyl acetoacetate and acetylacetone are preferable and acetylacetone is more preferable. The β-diketone compound and / or β-ketoester compound may be used individually or as a combination of two or more thereof. In the present invention, the β-diketone compound and / or the β-ketoester compound is used in an amount of preferably 2 mol or more, more preferably 3 to 20 mol, per mol of the metal chelate compound. If the addition amount is less than 2 moles, the composition may be poor in storage stability, which is undesirable.

The content of the hydrolyzate and / or partial condensate of the organosilane compound is preferably small in the surface layer which is a relatively thin film and large in the lower layer which is a thick film. In the case of a surface layer, such as a low refractive index layer, the content is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, in particular relative to the total solids content comprising the layer (the layer added thereto) More preferably, it is 1-10 mass%.

The amount added to the layers other than the low refractive index layer is from 0.001 to 50 mass%, more preferably from 0.01 to 20 mass%, particularly more preferably from 0.05 to 50 mass%, based on the total solids content including the layer (layer added thereto). 10 mass%, particularly preferably 0.1 to 5 mass%.

In the present invention, a composition comprising a hydrolyzate and / or partial condensate of a metal chelate compound and an organosilane compound is first prepared, to which β-diketone compound and / or β-ketoester compound are added, and the resulting solution Is introduced into the coating solution for at least one hard coating layer and low refractive index layer, and it is preferable to apply the coating solution.

In the low refractive index layer, the amount of organosilane sol component used is preferably 5 to 100% by mass, more preferably 5 to 40% by mass, particularly more preferably 8 to 35% by mass, relative to the fluorine-containing polymer. Especially preferably, it is 10-30 mass%. If the amount used is small, the effect of the present invention can hardly be obtained, while if the amount is too large, the refractive index may rise, and the form or surface state of the film may deteriorate, which is undesirable.

In the antireflective film of the present invention, an inorganic filler is preferably added to each layer on the transparent support. The inorganic fillers added to each layer may be the same or different, and it is desirable to select the type and amount added according to the required performance of each layer, such as refractive index, film strength, film thickness and coating property. .

As already described above, the inorganic filler used in the low refractive index layer preferably comprises silica fine particles.

The form of the inorganic filler for use in the present invention is not particularly limited, and for example, spherical, plate, fibrous, rod, amorphous and hollow are preferably used, but for the reason that good dispersibility is obtained. Sphere is preferred. The kind of the inorganic filler is not particularly limited either, but an amorphous filler is preferably used. Preference is given to including oxides of metals, nitrides, sulfides or halides, with metal oxides being more preferred. Examples of metal atoms are Na, Kr Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb and Ni. In order to obtain a transparent cured film, the average particle size of the inorganic filler is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, particularly more preferably 0.001 to 0.06 μm. Here, the average particle size of the particles is measured by Coulter Calculator.

In the present invention, the method of using the inorganic filler is not particularly limited, but, for example, the inorganic filler may be used in a dry state or dispersed in water or an organic solvent.

In the present invention, the dispersion stabilizer is preferably used mixed in the coating solution for forming each layer, to prevent aggregation and deposition of the inorganic filler. Examples of dispersion stabilizers that can be used include polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives, polyamides, phosphate esters, polyethers, surfactants, silane coupling agents and titanium coupling agents. Especially, since a film is hard after hardening, a silane coupling agent is preferable. The amount of the silane coupling agent added as the dispersion stabilizer is not particularly limited, but it is preferably 1 mass part or more per 100 mass parts of the inorganic filler. The addition method of the dispersion stabilizer is also not particularly limited, but the method of adding the dispersion stabilizer first after hydrolysis or mixing the silane coupling agent as the dispersion stabilizer with the inorganic filler and hydrolyzing and condensing the mixture Can be used. The latter method is preferred.

Suitable inorganic fillers for each layer are described below.

Low refractive index layer forming compositions for use in the present invention, usually in liquid form, are prepared by dissolving the copolymer as an essential component and, if desired, various additives and radical polymerization reaction initiators in a suitable solvent. Here, the concentration of the solid content is appropriately selected depending on the use, but is generally on the order of 0.01 to 60% by mass, preferably 0.5 to 50% by mass, more preferably 1 to 20% by mass.

As described above, in view of the film strength of the low refractive index layer, the addition of additives such as hardeners is not necessarily advantageous, but in view of the adhesion of gaps to high refractive index layers, etc., hardeners such as polyvalent (meth) acrylate compounds , Polyvalent epoxy compounds, polyisocyanate compounds, aminoplasts, polybasic acids and anhydrides thereof, or inorganic fine particles such as silica may be added in small amounts. When adding the said additive, the addition amount is 0-30 mass% with respect to the total solid content of a low refractive index layer film, More preferably, it is 0-20 mass%, Especially preferably, it is 0-10 mass%.

In order to impart slipperiness and resistance to soil, water and chemicals, known silicon-based or fluorine-based antifouling agents, sleeping agents and the like may be appropriately added. In the case of adding the additive, the additive is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, particularly more preferably 0.1 to 5% by mass, based on the total solids content of the lower n layer. It is added in the range of%.

Preferred examples of silicon-based compounds include compounds having a plurality of dimethylsilyloxy units as repeating units and having substituents at the chain ends and / or side chains. Structural units other than dimethylsilyloxy may be contained in the chain of the compound containing dimethylsilyloxy as a repeating unit. Multiple components are preferably present and the components can be the same or different. Preferred examples of the constituents include acyloyl group, metaacylyl group, vinyl group, aryl group, cinnamic group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It includes a group. The molecular weight is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, and most preferably 3,000 to 30,000. The silicon atom content of the silicon-based compound is not particularly limited, but is preferably 18.0 mass% or more, more preferably 25.0 to 37.8 mass%, and most preferably 30.0 to 37.0 mass%. Particularly preferred examples of silicon-based compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X- manufactured by Shin-Etsu Chemical Co., Ltd. 22-176D and X-22-1821 (all trade names) and FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083 and UMS-182 (all trade names) from Chisso Corporation, The present invention is not limited thereto.

The fluorine-based compound is preferably a compound having a fluoroalkyl group. The fluoroalkyl group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and is linear (eg, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, CH ₂ (CF ₂ ) ₈ CF ₃ and —CH ₂ CH ₂ (CF ₂ ) ₄ H), branched (eg CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ and CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H) or alicyclic (preferably a 5- or 5-membered ring, for example perfluorohexyl group, perfluoropentyl group, and Alkyl group substituted with the above group or may have an ether bond (eg, CH ₂ 0CH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ 0CH ₂ C ₄ F ₈ H, CH ₂ CH ₂ 0CH ₂ CH ₂ C ₈ F ₁₇ and CH ₂ CH ₂ 0CF ₂ CF ₂ 0CF ₂ CF ₂ H). Multiple fluoroalkyl groups can be included in one molecule.

The fluorine-based compound preferably further has substituents that contribute to bond formation or affinity with the low refractive index layer film. Plural substituents are preferably present and the substituents may be the same or different. Preferable examples of the substituent include an acyloyl group, methacryloyl group, vinyl group, acyl group, cinnamonyl group, epoxy group, oxetanyl group, hydroxyl group, polyoloxyalkylene group, carboxyl group and amino group. The fluorine-based compound may be a polymer or oligomer with a compound that does not contain fluorine atoms. The molecular weight is not particularly limited. The fluorine atom content of the fluorine-based compound is not particularly limited, but is preferably 20 mass% or more, more preferably 30 to 70 mass%, and most preferably 40 to 70 mass%. Preferred embodiments of the fluorine-based compound are R-2020, M-2020, R-3833 and M-3833 (all of which are trade names) manufactured by Daikin Kogyo Co., Ltd., and Dai-Nippon Ink & Chemicals, Inc. Megafac F-171, F-172, F-179A and DAYFENSA MCF-300 (all of which are trade names), although the invention is not limited thereto.

In order to impart properties such as dust protection properties and antistatic properties, dust inhibitors, antistatic agents and the like, such as known cationic surfactants or polyoxyalkylene-based compounds, may be appropriately added. In addition, the structural unit of the dust inhibitor or the antistatic agent may be included as part of the functional group in the silicon-based compound or the fluorine-based compound described above. In the case of adding the additive, the additive is in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, particularly more preferably 0.01 to 5% by mass relative to the total solids content of the lower n layer. Is added. Preferred examples of such compounds include, but are not limited to, Megafac F-150 (trade name) from Dai-Nippon Ink & Chemicals, Inc. and SH-3748 (trade name) from Toray Dow Corning.

The antiglare hard coat layer of the present invention is described below.

The antiglare hard coat layer is composed of a binder for imparting hard coating properties, matting particles for imparting antiglare properties, and an inorganic filler for imparting high refractive index and high strength and preventing crosslinking shrinkage.

The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, more preferably a polymer having a saturated hydrocarbon chain as the main chain.

The binder polymer also preferably has a crosslinked structure.

The binder polymer having a saturated hydrocarbon chain as its main chain is preferably a polymer of unsaturated monomers of ethylene. The binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure is preferably a (co) polymer of a monomer having at least two unsaturated groups of ethylene.

In order to provide a high refractive index, the monomer preferably comprises in its structure an aromatic ring or one or more atoms selected from the group consisting of halogen atoms (except fluorine), sulfur atoms, phosphorus atoms and nitrogen atoms.

Examples of monomers having two or more unsaturated groups of ethylene include polyhydric alcohols and (meth) acrylic acids (eg, ethylene glycol di (meth) acrylate 1,4-cyclohexane diacrylate, pentaerythritol tetra (meth) acrylic) Rate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate) Esters, vinylbenzenes and derivatives thereof (e.g., 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohex) Rice), and vinyl sulfones (e. G., Including divinyl sulfone), acrylamides (e.g., methylenebisacrylamide) and methacrylamide. The monomers can be used as a combination of two or more thereof.

Specific examples of the high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide and 4-methacryloxyphenyl-4'-methoxyphenylthioether. The monomers can also be used as combinations of two or more thereof.

The polymerization reaction of the monomer having an unsaturated group of ethylene can be carried out under irradiation of ionizing radiation or under heating in the presence of a photo-radical polymerization initiator or a heat-radical polymerization initiator.

Thus, the antireflective film prepares a coating solution comprising a monomer having an unsaturated group of ethylene, a photo- or heat-radical polymerization initiator, quenching particles, and an inorganic filler, applying the coating solution to a transparent support, and ionizing radiation Or by curing the coating solution through a polymerization reaction under heating.

Examples of photo-radical polymerization initiators include acetophenone, benzoin, benzophenone, phosphine oxide, ketal, anthraquinone, thioxanthone, azo compound, peroxide, 2,3-dialkyldione compound, disulfide compound, Fluoroamine compounds and aromatic sulfonium. Examples of acetophenones are 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-moropoly Nopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoin include benzoin benzenesulfonic acid ester, benzoin toluenesulfonic acid ester, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Also, various examples are described in Saishin UV Koka Gijutsu (Newest UV Curing Technology) , page 159, Kazuhiro Takausu (publisher), Gijutsu Joho Kyokai (publishing company) (1991), which are useful in the present invention.

Preferred examples of commercially available photodegradable photo-radical polymerization initiators include Irgacure (651, 184 and 907) from Nippon Ciba Geigy.

The photopolymerization reaction initiator is used in an amount of preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass per 100 parts by mass of the polyvalent monomer.

In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

Examples of heat-polymerization reaction initiators that can be used include organic or inorganic peroxides and organic azo or diazo compounds.

Specific examples of organic peroxides include benzoyl peroxide, halogen benzoyl peroxide, lauryl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide and butyl hydroperoxide. Specific examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate and potassium persulfate. Specific examples of azo compounds include 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile and 2-azo-bis-cyclohexane dinitrile. Specific examples of diazo compounds include diazoaminobenzenes and p-nitrobenzenediazonium.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyvalent epoxy compound. The ring-opening polymerization reaction of the polyvalent epoxy compound can be carried out under irradiation of ionizing radiation or heating in the presence of a photoacid generator or a heat-acid generator.

Thus, the antireflective film prepares a coating solution comprising a polyvalent epoxy compound, a photoacid or heat-acid generator, quenching particles, and an inorganic filler, applies the coating solution to a transparent support, and polymerizes under ionization radiation or heating. It can be formed by curing the coating solution through.

Instead of or in addition to monomers having two or more unsaturated groups of ethylene, monomers having a crosslinkable functional group are used so that the crosslinkable functional group is introduced into the polymer and a crosslinked structure is introduced into the binder polymer by reaction of the crosslinkable functional group. Can be.

Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups and active methylene groups. In addition, vinylsulfonic acid, acid anhydride, cyanoacrylate derivatives, melamine, etherified methylol, esters, urethanes or metal alkoxides such as tetramethoxysilane can be used as the monomer for introducing the crosslinked structure. Functional groups that exhibit crosslinking properties as a result of the decomposition reaction may also be used, such as block isocyanate groups. That is, the crosslinkable functional group for use in the present invention may be a group which does not directly cause a reaction but exhibits reactivity as a result of decomposition.

The binder polymer having the crosslinkable functional group may be coated and then heated, thereby forming a crosslinked structure.

To impart antiglare properties, the antiglare hard coat layer is larger than the filler particles and has a matting agent, for example inorganic compound particles or resin, having an average particle size of 1 to 10 μm, preferably 1.5 to 7.0 μm. Particles.

Preferred embodiments of the matting particles include inorganic compound particles such as silica particles and TiO ₂ particles; And resin particles such as acrylic particles, crosslinked acyl particles, polystyrene particles, crosslinked styrene particles, melamine resin particles and benzoguanamine resin particles. Among them, crosslinked styrene particles, crosslinked acrylic particles and silica particles are more preferable.

The shape of the matting particles may be completely spherical or amorphous.

In addition, two or more kinds of matting particles having different particle sizes may be mixed and used. Quenched particles with larger particle size can impart antiglare properties, and matted particles with smaller particle size can impart different optical properties. For example, if an antireflective film is attached to a high-definition display of 133 ppi or more, this should not cause a problem called glare in optical performance. Glare is due to the phenomenon that the pixels are enlarged or reduced due to the projections (contributing to the antiglare characteristics) present on the film surface, and the uniformity of the brightness is lost. Such glare can be greatly improved by using in combination with matting particles having a smaller size than matting particles for imparting antiglare properties and having a refractive index different from that of the binder.

The particle size distribution of the matting particles is most preferably monodisperse. Each particle preferably has the same particle size as possible. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the coarse particles in the total number of particles are preferably 1% or less, more preferably 0.1% or less, or in particular More preferably, it is 0.01% or less. Quenching particles having the above particle size distribution are obtained by performing fractionation after a general polymerization reaction. By increasing the number of sorting operations or enhancing the degree of sorting, a quencher having a more desirable distribution can be obtained.

The matting particles are included in the antiglare hard coating layer such that the amount of matting particles of the antiglare hard coat layer to be formed is 10 to 1,000 mg / m 2, more preferably 100 to 700 mg / m 2.

The particle size distribution of quenched particles is measured by the Coulter calculator method, and the measured distribution is converted to the particle number distribution.

In addition to the matt particles described above, the antiglare hard coat layer preferably comprises an oxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, indium, zinc, tin and antimony, and is 0.2 μm Or less, preferably including an inorganic filler having an average particle size of 0.1 μm or less, more preferably 0.06 μm or less, to increase the refractive index of the antiglare layer.

Conversely, in order to increase the refractive index difference from the matting particles, it is also desirable to keep the refractive index of the layer lower using oxides of silicon of the antiglare hard coat layer using the high refractive index matting particles. Preferred particle sizes are the same as those of the inorganic filler.

Specific examples of inorganic fillers for use in the antiglare hard coat layer include TiO ₂ , ZrO ₂ , A1 ₂ 0 ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . Among the inorganic fillers, TiO ₂ and ZrO ₂ are preferable from the viewpoint of achieving high refractive index. The surface of the inorganic filler is preferably treated with silane coupling or titanium coupling. Surface treating agents having functional groups capable of reacting with the kind of binder on the filler surface are preferably used.

The amount of the inorganic filler added is preferably 10 to 90%, more preferably 20 to 80%, particularly more preferably 30 to 75%, based on the total mass of the antiglare hard coat layer.

The filler has a particle size sufficiently smaller than the wavelength of light, and thus does not cause scattering, and the dispersion obtained by dispersing the filler in the binder polymer behaves as an optically uniform material.

The bulk refractive index of the binder and inorganic filler mixture in the antiglare hard coat layer is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. The refractive index in the above range can be achieved by appropriately selecting the ratio of the type and amount of the binder and the inorganic filler. The method of determining can be easily known in advance by experiment.

In the present invention, in order to ensure the surface state uniformity of the antiglare hard coating layer, in particular, by preventing coating nonuniformity, dry nonuniformity, spot defects, etc., one of the fluorine-containing surfactant and the silicon-containing surfactant is Or both are introduced into the coating composition for formation of the antiglare layer. In particular, the fluorine-containing surfactant is preferred because the effect of improving the surface defects, such as coating nonuniformity, dry nonuniformity and spot defects of the antireflection film of the present invention can be achieved by adding it in a small amount.

In order to enhance the surface state uniformity and thus improve productivity while imparting high-speed coating property, the surfactant is added.

Preferred examples of fluorine-containing surfactants include fluoro-aliphatic group-containing copolymers (sometimes simply referred to as "fluorine based polymers"). As the fluorine-based polymer, copolymers of acrylic resins and methacryl resins each comprising a repeating unit corresponding to the following monomer (i) and a repeating unit corresponding to the following monomer (ii), and a vinyl-based monomer copolymerizable therewith are useful. Do.

(i) a fluoro-aliphatic group-containing monomer represented by Formula 5 below:

In formula (5), R ¹¹ represents a methyl group, X represents an oxygen atom, a sulfur atom or -N (R ¹² )-, m represents an integer of 1 to 6, n represents an integer of 2 or 3, R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

In formula (5), m is an integer from 1 to 6, more preferably 2.

In Formula 5, n is an integer of 1 to 3, a mixture of n = 1 to 3 can also be used.

(ii) a monomer copolymerizable with monomer (i) represented by the following formula (6):

In formula (6), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom, or -N (R ¹⁵ )-, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, A propyl group or a butyl group, Preferably it represents a hydrogen atom or a methyl group. Y is preferably an oxygen atom, -N (H)-or -N (CH ₃ )-.

R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent of the alkyl group represented by R ¹⁴ include hydroxyl group, alkylcarbonyl group, arylcarbonyl group, carboxyl group, alkylether group, arylether group, halogen atom such as fluorine atom, chlorine atom and bromine atom, nitro group, cyano group and Although amino groups are included, the present invention is not limited thereto. Suitable examples of linear, branched or cyclic alkyl groups having 4 to 20 carbon atoms include linear or branched butyl groups, linear or branched pentyl groups, linear or branched hexyl groups, linear or branched heptyl groups, linear or branched octyl groups , Linear or branched nonyl groups, linear or branched decyl groups, linear or branched undecyl groups, linear or branched dodecyl groups, linear or branched tridecyl groups, linear or branched tetradecyl groups, linear or branched penta groups Decyl groups, linear or branched octadecyl groups, linear or branched eicosanyl groups, monocyclic cycloalkyl groups such as cyclohexyl and cycloheptyl groups, and polycyclic cycloalkyl groups such as bicycloheptyl groups, bicyclodecyl groups , Tricycloundecyl group, tetracycloundecyl group, adamantyl group, norbornyl group and tetracyclodecyl group.

The amount of the fluoro-aliphatic group-containing monomer represented by the formula (4) used in the fluorine-based polymer for use in the present invention is 10 mol% or more, preferably 15 to 70 mol, based on each monomer of the fluorine-based polymer. %, More preferably 20 to 60 mol%.

The mass average molecular weight of the fluorine-based polymer for use in the present invention is preferably 3,000 to 100,000, more preferably 5,000 to 80,000.

The amount of the fluorine-based polymer to be used in the present invention is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, particularly preferably 0.01 to 1% by mass relative to the coating solution. If the amount of the fluorine-based polymer added is less than 0.001% by mass, the effect is insufficient, whereas if the amount of the fluorine-based polymer added is higher than 5% by mass, the coating film is not sufficiently dry or the performance as a coating film (eg, reflectance and scratch resistance) is adversely affected. .

Specific examples of the structure of the fluorine-based polymer for use in the present invention are described below, but the present invention is not limited thereto. In the formula, numbers represent molar ratios of the monomer components and Mw represents mass average molecular weight.

However, when the above-described fluorine-based polymer is used, functional groups containing F atoms are collected on the surface of the hard coating layer, and as a result, the surface energy of the hard coating layer is reduced, so that the low refractive index layer is on the hard coating layer. Overcoating causes a problem of deteriorating antireflection performance. This is expected to occur because the wettability of the coating composition for the formation of the low refractive index layer is reduced and the fine nonuniformity that is not measurably visible in the film thickness of the low refractive index layer is further enhanced. In order to solve this problem, the surface energy of the hard coat layer is preferably adjusted to 20 to 50 mN · m ⁻¹ , more preferably 30 to 40 mN · m ⁻¹ by adjusting the structure and the addition amount of the fluoropolymer. Was found to be effective. In order to achieve the surface energy, as measured by X-ray photoelectron spectrometer, F / C, which is the ratio of peaks due to fluorine atoms / peaks due to carbon atoms, should be 0.1 to 1.5.

In addition, when the surface energy does not decrease at the time of overcoating of the low refractive index layer on the hard coating layer, deterioration of the antireflection performance can be prevented. In the coating of the hard coating layer, by using a fluorine based polymer, the surface tension of the coating solution is reduced, thereby enhancing the uniformity of the surface state and maintaining high productivity by high-speed coating, and after the coating of the hard coating layer, surface treatment, Reduction of surface free energy is prevented, for example, by using corona treatment, UV treatment, heat treatment, saponification treatment or solvent treatment, preferably corona treatment, whereby the surface energy of the hard coating layer prior to the coating of the low refractive index layer is prevented. It can be adjusted within and thus achieves its purpose.

The film thickness of the antiglare hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

The inventors also confirmed that the scattering intensity distribution measured by the goniophotometer is associated with an improvement in viewing angle. That is, since the light emitted from the halo is further diffused by the light-diffusion film provided on the polarizing plate surface in the field of view, the viewing angle characteristic is further improved. However, if the light is excessively diffused, scattering at the rear side increases and brightness at the front side decreases or excessively large scattering occurs, causing problems such as deterioration of a clear image. Therefore, the scattered intensity distribution must be adjusted to a specific range. As a result of extensive investigations, in order to obtain the desired visibility properties, the scattering luminous intensity at 30 °, in particular associated with the viewing angle-improving effect, is preferably 0.01 to 0.2%, more than the luminous intensity at exit angle 0 ° in the scattered light profile. It is preferably 0.02 to 0.15%, particularly more preferably 0.03 to 0.1%.

The scattered light profile of the resulting light-scattering film can be measured using a Murakami Color Research Laboratory, an Autogoniophotometer, Model GP-5.

[High refractive index layer]

In the antireflection film of the present invention, in order to give higher antireflection performance, a high refractive index layer may also be preferably used.

(Inorganic fine particles mainly containing titanium dioxide).

The high refractive index layer for use in the present invention contains inorganic fine particles comprising as a main component titanium dioxide containing at least one element selected from cobalt, aluminum and zirconium. A main component means the largest component among the components whose content (mass%) comprises a particle | grain.

The refractive index of the high refractive index layer for use in the present invention is 1.55 to 2.40, which is a layer called a high refractive index layer or a medium refractive index layer, but in the present invention, these layers are often collectively referred to as a high refractive index layer.

The inorganic fine particles mainly containing titanium dioxide for use in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, particularly more preferably 2.20 to 2.80.

The mass average major particle size of the inorganic fine particles mainly containing titanium dioxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, particularly more preferably 1 to 100 nm, particularly preferably 1 to 1 80 nm.

The particle size of the inorganic fine particles can be measured by light scattering method or electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably 20 to 200 m ² / g, and most preferably 30 to 150 m ² / g.

In the crystal surface of the inorganic fine particles mainly containing titanium dioxide, the main component is preferably rutile structure, rutile / alumina mixed crystal, anatase structure or amorphous structure, preferably rutile structure. A main component means the most component among the components in which a component (mass%) comprises particle | grains.

By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the inorganic fine particles mainly containing titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, and the present invention The weather resistance of the high refractive index layer for use in can be improved.

The element is preferably Co (cobalt). Preference is also given to the use of a combination of two or more elements.

Each component of Co (cobalt), Al (aluminum) and Zr (zirconium) is preferably 0.05 to 30 mass%, more preferably 0.1 to 10 mass%, particularly more preferably 0.2 to Ti (titanium). To 7% by mass, particularly preferably 0.3 to 5% by mass, and most preferably 0.5 to 3% by mass.

Co (cobalt), Al (aluminum) and Zr (zirconium) may be present on one or more of the surface or inside of the inorganic fine particles mainly containing titanium dioxide, but the element is an inorganic fine particle mainly containing titanium dioxide. It is preferable to exist inside of, and more preferably, to exist in both inside and the surface.

Co (cobalt), Al (aluminum) and Zr (zirconium) can be prepared (eg, doped) to be present inside the inorganic fine particles which mainly comprise titanium dioxide by various methods. Examples of such methods are ion injection method (see Yasushi Aoki, Vol. 18, No. 5, pp. 262-268 (1998)) and JP-A-11-263620, JP-T -11-512336 (the term "JP-T" as used herein means a published Japanese translation of a PCT patent application), the methods described in EP-A-0335773 and JP-A-5-330825.

A method of introducing Co (cobalt), Al (aluminum) and Zr (zirconium) in the particle formation process for forming inorganic fine particles mainly containing titanium dioxide (e.g., JP-T-11-512336, EP- Particular preference is given to A-0335773 and JP-A-5-330825.

Co (cobalt), Al (aluminum) or Zr (zirconium) is also preferably present in oxide form.

The inorganic fine particles mainly containing titanium dioxide may further contain other elements depending on the purpose. Other elements may be contained as impurities. Examples of other elements are Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Mg, Si, P and S.

The inorganic fine particles mainly containing titanium dioxide used in the present invention may be surface-treated. Surface treatment is carried out by using an inorganic compound or an organic compound. Examples of inorganic compounds for use in surface treatment include cobalt-containing inorganic compounds (eg, CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ ), aluminum-containing inorganic compounds (eg, Al ₂ O ₃ , Al (OH) ₃ ), zirconium-containing inorganic compounds (eg ZrO ₂ , Zr (OH) ₄ ), silicon-containing inorganic compounds (eg SiO ₂ ) and iron-containing inorganic compounds (eg , Fe ₂ O ₃ ).

Of these, cobalt-containing inorganic compounds, aluminum-containing inorganic compounds and zirconium-containing inorganic compounds are preferred, and cobalt-containing inorganic compounds, Al (OH) ₃ and Zr (OH) ₄ are most preferred.

Examples of organic compounds for use in surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Of these, the silane coupling agent is most preferred. In particular, surface treatment with the organosilane compound represented by the formula (3) or a derivative thereof is preferable.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium and tetraisopropoxy titanium and Preneact (eg KR-TTS, KR-46B, KR-55 and KR-41B, Ajinomoto Co., Inc.).

Preferred examples of organic compounds for use in the present invention include polyols, alkanolamines and other organic compounds having nonionic groups. Among these, the organic compound which has a carboxyl group, a sulfonic acid group, or a phosphoric acid group is more preferable.

Stearic acid, lauric acid, oleic acid, linoleic acid and linolenic acid are preferably used.

The organic compound for use in the surface treatment preferably further has a crosslinkable or polymerizable functional group. Examples of crosslinkable or polymerizable functional groups include unsaturated groups of ethylene (e.g. (meth) acrylic, allyl, styryl, vinyloxy) capable of addition reaction / polymerization by radicals, cationic polymerizable groups (e.g. For example epoxy, oxanyl, vinyloxy) and polycondensation reactive groups (eg hydrolyzable silyl groups, N-methylol).

These surface treatments may be used in combination of two or more thereof. Particular preference is given to using a combination of aluminum-containing organic compounds and zirconium-containing inorganic compounds.

As described in JP-A-2001-166104, the inorganic fine particles mainly comprising titanium dioxide for use in the present invention may have a core / shell structure by surface treatment.

The form of the inorganic fine particles mainly containing titanium dioxide contained in the high refractive index layer is preferably gravel, spherical, cubic, spindle form or amorphous form, more preferably amorphous or fusiform. .

(Dispersant)

In order to disperse the inorganic fine particles mainly comprising titanium dioxide, which are used in the refractive index layer of the present invention, a dispersant may be used.

In order to disperse the inorganic fine particles mainly containing titanium dioxide used in the present invention, a dispersant having an anionic group is preferably used.

As anionic groups, groups having acidic protons, such as carboxyl groups, sulfonic acid groups (and sulfo groups), phosphoric acid groups (and phosphono groups) and sulfonamide groups and salts thereof are effective. Among these, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and its salt are preferable, and a carboxyl group and a phosphoric acid group are more preferable. The number of anionic groups contained per mole of dispersant is one or more.

In order to further enhance the dispersibility of the inorganic fine particles, a plurality of anionic groups may be contained. The average number of anionic groups is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. In addition, various kinds of anionic groups may be contained in one molecule of the dispersant.

The dispersant preferably further comprises a crosslinkable or polymerizable functional group. Examples of crosslinkable or polymerizable functional groups are unsaturated groups of ethylene (e.g. (meth) acryloyl, allyl, styryl, vinyloxy) capable of addition reaction / polymerization by radicals, cationic polymerizable groups ( For example, epoxy, oxanyl, vinyloxy) and polycondensation reactive groups (eg hydrolyzable silyl groups, N-methylol). Among these, the functional group which has an unsaturated group of ethylene is preferable.

The dispersant used to disperse the inorganic fine particles mainly comprising titanium dioxide, which is used in the high refractive index layer of the present invention, preferably has an anionic group and a crosslinkable or polymerizable functional group, and at the same time is crosslinkable on the side chain. Or a dispersant having a polymerizable functional group.

The mass average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and at the same time having a crosslinkable or polymerizable functional group on the side chain is not particularly limited, but it is preferably 1,000 or more, more preferably Is 2,000 to 1,000,000, particularly more preferably 5,000 to 200,000, particularly preferably 10,000 to 100,000.

As anionic groups, groups having acidic protons, such as carboxyl groups, sulfonic acid groups (and sulfo groups), phosphoric acid groups (and phosphono groups) and sulfonamide groups and salts thereof are effective. Among these, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and its salt are preferable, and a carboxyl group and a phosphoric acid group are more preferable. The number of anionic groups contained per mole of dispersant is preferably on average 2 or more, more preferably 5 or more and even more preferably 10 or more. In addition, many kinds of anionic groups may be contained in one molecule of the dispersant.

Dispersants having anionic groups and crosslinkable or polymerizable functional groups and at the same time having crosslinkable or polymerizable functional groups on the side chains have anionic groups on the side chains or ends.

Particular preference is given to dispersants having anionic groups on the side chains. In dispersants having anionic groups on the side chains, the proportion of anionic group-containing repeat units is 10 ^-4 to 100 mole%, preferably 1 to 50 mole%, particularly more preferably 5 to 1, for all repeating units. 20 mol%.

Examples of crosslinkable or polymerizable functional groups include unsaturated groups of ethylene (e.g. (meth) acrylic, allyl, styryl, vinyloxy) capable of addition reaction / polymerization by radicals, cationic polymerizable groups (e.g. For example epoxy, oxanyl, vinyloxy) and polycondensation reactive groups (eg hydrolyzable silyl groups, N-methylol). Among these, the functional group which has an unsaturated group of ethylene is preferable.

The number of crosslinkable or polymerizable functional groups contained per mole of dispersant is, on average, preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. In addition, many kinds of crosslinkable or polymerizable functional groups may be included in one molecule of the dispersant.

In preferred dispersants for use in the present invention, examples of repeating units having unsaturated groups of ethylene on the side chain which may be used include poly-1,2-butadiene structures, poly-1,2-isoprene structures and certain residues (- Amide repeat units or (meth) acrylic acid esters combined with COOR or R groups of -CONHR). Examples of specific residues (R groups) include-(CH ₂ ) _n -CR ²¹ = CR ²² R ²³ ,-(CH ₂ O) _n -CH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ CH ₂ O) _n -OCH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ²¹ = CR ²² R ²³ ,-(CH ₂ ) _n -O-CO-CR ²¹ = CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X wherein R ²¹ to R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or an aryloxy group, and R ²¹ may combine with R ²² or R ²³ to form a ring, n is an integer from 1 to 10, and X is a dicyclopentadienyl residue. Specific examples of ester moieties include -CH ₂ CH = CH ₂ (corresponding to the polymer of allyl (meth) acrylate described in JP-A-64-17047), -CH ₂ CH ₂ O-CH ₂ CH = CH ₂ ,- CH ₂ CH ₂ OCOCH = CH ₂ , -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H ₅ , -CH _{2 CH 2 OCOCH = CH-C 6} H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and -CH ₂ CH ₂ OX and a (wherein, X is being dicyclopentadienyl residue). Specific examples of amide moieties include -CH ₂ CH = CH ₂ , -CH ₂ CH ₂ -Y (where Y is a 1-cyclohexenyl residue), CH ₂ CH ₂ -OCO-CH = CH ₂ and -CH ₂ CH ₂ -OCO-C (CH ₃ ) = CH ₂ .

In a dispersant having an unsaturated group of ethylene, free radicals (polymerization initiation radicals or growth radicals in the polymerization step of the polymerizable compound) are added to the unsaturated bond group to add polymerization directly to intermolecular molecules or through chain polymerization of the polymerizable compound. As a result, intermolecular crosslinking is formed, thereby completing curing. Alternatively, intramolecular atoms (e.g., hydrogen atoms on carbon atoms adjacent to unsaturated bond groups) are removed with free radicals to form polymer radicals, and the polymer radicals are bonded to each other to form intermolecular crosslinks, thereby curing To complete.

The crosslinkable or polymerizable functional group-containing unit may constitute all repeating units except for the anionic group-containing repeating unit, but is preferably 5 to 50 mol%, more preferably 5 to 30 of all crosslinking or repeating units. Account for mole percent.

Preferred dispersants of the invention may be copolymers with suitable monomers other than monomers having crosslinkable or polymerizable functional groups and anionic groups. The copolymerization component is not particularly limited but is selected from various aspects, such as dispersion stability, affinity with other monomer components, and strength of the formed film. Preferred examples thereof include methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate and styrene.

Preferred dispersants of the present invention are not particularly limited thereto, but are preferably block copolymers or random copolymers, and in view of cost and easy synthesis, random copolymers are more preferable.

Specific examples of the dispersant preferably used in the present invention are described below, but the dispersant for use in the present invention is not limited thereto. Unless stated otherwise, they are random copolymers.

The amount of dispersant used is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and most preferably 5 to 20% by mass relative to the inorganic fine particles. It is also possible to use two or more dispersants in combination.

[High refractive index layer and formation method thereof]

Inorganic fine particles for use in the high refractive index layer, mainly comprising titanium dioxide, are used in a dispersed state for the formation of the high refractive index layer.

The inorganic fine particles are dispersed in the dispersion medium in the presence of the dispersant described above.

The dispersion medium is preferably a liquid having a boiling point of 60 to 170 ° C. Examples of dispersion media include water, alcohols (eg methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (Eg methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg benzene, toluene, xylene), amides (eg dimethylformamide, dimethylacetamide, n-methylpyrroli) Don), ethers (eg diethyl ether, dioxane, tetrahydrofuran) and ether alcohols (eg 1-methoxy-2-propanol). Among them, preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol, more preferably methyl ethyl ketone, methyl isobutyl ketone and cyclo hexanone.

Inorganic fine particles are dispersed using a dispersion mechanism. Examples of dispersion mechanisms include sand grinder mills (eg, bead mills with pins), high speed impellers, pebble mills, roller mills, adjusters and colloid mills. Especially, a sand grinder mill and a high speed impeller are preferable. In addition, preliminary dispersion processing can be performed. Examples of dispersion mechanisms for use in predispersion processing include ball mills, three-roll mills, kneaders and extruders.

The inorganic fine particles are preferably dispersed in the dispersion medium to have the smallest possible particle size. The mass average particle size is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and even more preferably 10 to 80 nm.

By dispersing the inorganic fine particles into small particle sizes of 200 nm or less, a high refractive index layer can be formed without compromising transparency.

The high refractive index layer for use in the present invention is preferably formed as follows. To the dispersion solution obtained by dispersing the inorganic fine particles in the dispersion medium, a binder precursor (the same as used for the antiglare hard coat layer), a photopolymerization initiator, and the like, which are necessary for matrix formation, are preferably further added, , Preparing a coating composition for forming a high refractive index layer, coating the obtained coating composition for forming a high refractive index layer on a transparent support, and crosslinking an ionized radiation-curable compound (for example, a polyvalent monomer or a polyvalent oligomer) Curing through a reaction or polymerization reaction.

Simultaneously with or after the coating of the high refractive index layer, the binder of the layer is preferably crosslinked or polymerized with a dispersant.

The binder of the high refractive index layer thus formed takes the form in which anionic groups of the dispersant are introduced into the binder after the crosslinking or polymerization reaction between the above-described preferred dispersant and the ionizing radiation-curable polyvalent monomer or oligomer. Moreover, in the binder of the high refractive index layer, the anionic groups have the function of maintaining the dispersed state of the inorganic fine particles, and the crosslinked or polymerized structure imparts the film forming ability to the binder, and as a result, includes the inorganic fine particles. Physical strength and chemical resistance and weather resistance of the high refractive index layer are improved.

For the polymerization reaction of the photopolymerizable polyvalent monomer, a photopolymerization reaction is preferably used. The photopolymerization initiator is preferably a photo-radical polymerization initiator or a photo-cationic polymerization initiator, more preferably a photo-radical polymerization initiator.

Examples of photo-radical polymerization initiators that can be used include those described above for the antiglare hard coat layer.

In the high refractive index layer, the binder preferably further has silanol groups. By having silanol groups in the binder, the physical strength and chemical and weather resistance of the high refractive index layer are further improved.

For example, a compound having a crosslinkable or polymerizable functional group, represented by Formula 3, is added to a coating composition for forming a high refractive index layer, and the coating composition is applied onto a transparent support, and the aforementioned dispersant, polyvalent By crosslinking or polymerizing the monomer or oligomer and the compound represented by the formula (3), the silanol group can be introduced into the binder.

In the high refractive index layer, the binder also preferably has an amino group or a quaternary ammonium group.

The binder having an amino group or a quaternary ammonium group of the high refractive index layer, for example, adds a monomer having a crosslinkable or polymerizable functional group and an amino group or a quaternary ammonium group to the coating composition for forming the high refractive index layer, and adds the coating composition It can be formed by applying on a transparent support and crosslinking or polymerizing with the above-mentioned dispersing agent and a polyvalent monomer or oligomer.

The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid of the inorganic fine particles in the coating composition. Furthermore, after coating, the monomers can be crosslinked or polymerized with dispersants and polyvalent monomers or oligomers to form binders, thereby maintaining good dispersibility of the inorganic fine particles in the high refractive index layer, physical strength and chemical resistance And a high cutting rate layer excellent in weather resistance can be produced.

Preferable examples of the monomer having an amino group or a quaternary ammonium group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and hydroxypropyltrimethylammonium chloride (meth) acrylate. And dimethylallyl ammonium chloride.

The amount of the monomer having an amino group or a quaternary ammonium group is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, particularly preferably 3 to 20% by mass relative to the dispersant. When the binder is formed by a crosslinking or polymerization reaction simultaneously with or after the coating of the high refractive index layer, the monomer can effectively function before the coating of the high refractive index layer.

The binder formed after crosslinking or polymerization has a structure in which the polymer backbone is crosslinked or polymerized. Examples of polymer backbones include polyolefins (saturated hydrocarbons), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides, and melamine resins. Especially, a polyolefin main chain, a polyether main chain, and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is the most preferable.

The polyolepene backbone includes saturated hydrocarbons. The polyolefin backbone is obtained by, for example, addition polymerization of unsaturated polymerizable groups. In the polyether backbone, repeating units are linked via ether bonds (-O-). The polyether main chain is obtained by, for example, a ring-opening polymerization reaction of an epoxy group. In the polyurea backbone, repeating units are joined via urea bonds (-NH-CO-NH-). The polyurea main chain is obtained by, for example, a condensation polymerization reaction of an isocyanate group and an amino group. In the polyurethane backbone, repeating units are bonded via urethane bonds (-NH-CO-O-). The polyurethane main chain is obtained by, for example, a condensation polymerization reaction of isocyanate groups and hydroxyl groups (including N-methylol groups). In the polyester backbone, repeating units are bonded via ester bonds (-CO-O-). The polyester main chain is obtained by, for example, a condensation polymerization reaction of a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine backbone, repeating units are bonded via an imino group (-NH-). The polyamine main chain is obtained by, for example, a ring-opening polymerization reaction of ethyleneimine groups. In the polyamide backbone, repeating units are bound via amido groups (-NH-CO-). Polyamide backbones are obtained, for example, by reaction of isocyanate groups and carboxyl groups (including acid halide groups). The melamine resin backbone is obtained by, for example, a condensation polymerization reaction of a triazine group (e.g. melamine) and an aldehyde (e.g. formaldehyde). Incidentally, in the melamine resin, the main chain itself has a crosslinked or polymerized structure.

The anionic group is preferably bound as a side chain to the backbone of the binder via a linking group.

The linking group connecting the anionic group and the binder backbone is preferably a divalent group selected from -CO-, -O-, alkylene groups, arylene groups and combinations thereof. The crosslinked or polymerized structure forms chemical bonds (preferably covalent bonds) of two or more backbones, and preferably forms covalent bonds of three or more backbones. The crosslinked or polymerized structure preferably comprises a divalent or higher valence group selected from -CO-, -O-, -S-, nitrogen atoms, phosphorus atoms, aliphatic residues, aromatic residues and combinations thereof.

The binder is preferably a copolymer comprising repeating units having anionic groups and repeating units having a crosslinked or polymerized structure. In the copolymer, the proportion of repeating units having anionic groups is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups. In the copolymer, the proportion of repeating units having a crosslinked or polymerized structure is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The repeat units of the binder may have both anionic groups and crosslinked or polymerized structures. In addition, the binder may comprise other repeating units (repeating units having no anionic groups or crosslinked or polymerized units).

Such other repeating units are preferably repeating units having a silanol group, an amino group or a quaternary ammonium group.

In repeat units having silanol groups, silanol groups are bonded directly to the binder backbone or through the linking group to the backbone. The silanol groups are preferably bonded as side chains to the main chain via linking groups. The linking group connecting the silanol group and the binder main chain is preferably a divalent group selected from -CO-, -O-, an alkylene group, an arylene group and combinations thereof. In the case where the binder comprises repeating units having silanol groups, the proportion of repeating units is preferably 2 to 98 mol%, more preferably 4 to 96 mol%, and most preferably 6 to 94 mol%.

In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is bonded directly to the binder backbone or through the linking group to the backbone. An amino group or quaternary ammonium group is preferably bonded as a side chain to the main chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, tertiary amino group or quaternary ammonium group, more preferably tertiary amino group or quaternary ammonium group. The group bonded to the nitrogen atom of the secondary or tertiary amino group or the quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group connecting the amino group or the quaternary ammonium group to the binder main chain is preferably a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group and combinations thereof. When the binder comprises a repeating unit having an amino group or a quaternary ammonium group, the proportion of the repeating unit is preferably 0.1 to 32 mol%, more preferably 0.5 to 30 mol%, and most preferably 1 to 1 mol. 28 mol%.

Incidentally, the same effect can be obtained even when the silanol group, amino group or quaternary ammonium group is contained in a repeating unit having an anionic group or a repeating unit having a crosslinked or polymerized structure.

The crosslinked or polymerized binder is preferably formed by a crosslinking or polymerization reaction simultaneously with or after the coating of the composition for the formation of the high refractive index layer.

The inorganic fine particles have an effect of adjusting the refractive index of the high refractive index layer, and also have a function of suppressing cure shrinkage.

The inorganic fine particles are preferably dispersed in the high refractive index layer and have as small particle size as possible. The mass average particle size is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm.

By dispersing the inorganic fine particles into small particle sizes of 200 nm or less, high refractive index layers can be formed without compromising transparency.

The content of the inorganic fine particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, particularly preferably 15 to 75% by mass relative to the mass of the high refractive index layer. In the high refractive index layer, two or more kinds of inorganic fine particles may be used in combination.

In the case of having a low refractive index layer on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than that of the transparent support.

In the high refractive index layer, an ionizing radiation-curable compound comprising an aromatic ring, an ionizing radiation-curable compound comprising a halogen element except for fluorine (eg, Br, I, Cl), or atoms such as S, N and P Also preferably used are binders obtained by crosslinking or polymerization reactions of ionizing radiation-curable compounds comprising a.

In forming an antireflection film by forming a low refractive index layer on the high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, particularly more preferably 1.65 to 2.10, and most Preferably it is 1.80-2.00.

The high refractive index layer, in addition to the aforementioned components (e.g., inorganic fine particles, polymerization initiators, photosensitizers), may contain resins, surfactants, antistatic agents, coupling agents, thickeners, anti-colorants, colorants (e.g., pigments, Dyes), antifoams, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, tackifiers, polymerization inhibitors, antioxidants, surface modifiers, electrically conductive metal fine particles, and the like. .

The film thickness of the high refractive index layer may be appropriately selected depending on the intended use. When the high refractive index layer is used as the optical interference layer described below, the film thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, particularly more preferably 60 to 150 nm.

In the formation of the high refractive index layer, the crosslinking or polymerization reaction of the ionizing radiation-curable compound is preferably carried out in an atmosphere of oxygen concentration of 10 vol% or less.

By forming a high refractive index layer in an atmosphere of oxygen concentration of 10% by volume or less, the physical strength and chemical resistance and weather resistance of the refractive index layer can be improved, and moreover, the adhesion between the high refractive index layer and the layer adjacent to the high refractive index layer This can be improved.

The high refractive index layer is ionized in an atmosphere of an oxygen concentration of preferably at most 6% by volume, more preferably at most 4% by volume, particularly more preferably at most 2% by volume, and most preferably at most 1% by volume. It is formed by carrying out the crosslinking or polymerization reaction of the radiation-curable compound.

The oxygen concentration may preferably be adjusted to 10% by volume or less by replacing air (nitrogen concentration: about 79% by volume, oxygen concentration: about 21% by volume) with another gas, more preferably nitrogen (nitrogen scrubbing). have.

The strength of the high refractive index layer is preferably at least H, more preferably at least 2H, and most preferably at least 3H, as measured according to the pencil strength test according to JIS K5400.

Moreover, in the Taber test according to JIS K5400, the wear loss of the specimen between before and after the test is preferably smaller.

If the high refractive index layer does not contain particles that impart antiglare function, the haze of the layer is preferably lower, specifically less than 5%, more preferably less than 3%, particularly more preferred. Preferably less than 1%.

The high refractive index layer is preferably formed on the transparent support either directly or through another layer.

[Hard coating layer]

In order to impart physical strength to the antireflection film, as the hard coating layer, a so-called smooth hard coating layer having no antiglare property is also preferably used. The smooth hard coating layer is provided on the transparent support surface, preferably between the transparent support and the antiglare hard coating layer or between the transparent support and the high refractive index layer.

The hard coat layer is preferably formed by crosslinking or polymerization of the ionizing radiation-curable compound. For example, a coating composition containing an ionizing radiation-curable polyvalent monomer or oligomer may be coated on a transparent support, and the hard coating layer may be formed by crosslinking or polymerizing the polyvalent monomer or oligomer.

The functional group of the ionized radiation-curable polyvalent monomer or oligomer is preferably a photopolymerizable functional group, an electron beam polymerizable functional group or a radiation polymerizable functional group, more preferably a photopolymerizable functional group.

Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group and allyl group. Among these, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyvalent monomer having a photopolymerizable functional group include those described above as examples for use in the high refractive index layer. It is preferable that a monomer superposes | polymerizes using a photoinitiator or a photosensitive agent. The photopolymerization reaction is preferably carried out by ultraviolet irradiation after the hard coat layer is coated and dried.

The hard coat layer preferably contains inorganic fine particles having a major average particle size of 200 nm or less. As used herein, the average particle size is the mass average particle size. By fixing the main average particle size below 200 nm, a hard coat layer can be formed without compromising transparency.

The inorganic fine particles increase the strength of the hard coating layer and at the same time have a function of suppressing the curing shrinkage of the coating layer. Inorganic fine particles are also added for the purpose of controlling the refractive index of the hard coat layer.

Examples of the inorganic fine particles include silicon dioxide, aluminum oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, titanium dioxide, in addition to the inorganic fine particles described above as examples used for the refractive index layer, Fine particles of zirconium oxide, tin oxide, ITO and zinc oxide. Of these, silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO and zinc oxide are preferred.

The main average particle size of the inorganic fine particles is preferably 5 to 200 nm, more preferably 10 to 150 nm, particularly more preferably 20 to 100 nm, particularly preferably 20 to 50 nm.

The inorganic fine particles are preferably dispersed in the hard coat layer in order to have the smallest particle size possible.

The particle size of the inorganic fine particles in the hard coating layer is an average particle size, preferably 5 to 300 nm, more preferably 10 to 200 nm, particularly more preferably 20 to 150 nm, particularly preferably 20 to 80 nm.

The content of the inorganic fine particles in the hard coating layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, particularly preferably 15 to 75% by mass relative to the total mass of the hard coating layer. .

The film thickness of the hard coat layer may be appropriately selected depending on the intended use. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm, particularly more preferably 0.7 to 5 μm.

The strength of the hard coat layer, as measured by a pencil strength test according to JIS K5400, is preferably at least H, more preferably at least 2H, and most preferably at least 3H.

Further, in the burn test according to JIS K5400, it is preferable that the wear loss of the specimen between before and after the test is smaller.

In the case where the hard coating layer is formed by the crosslinking or polymerization reaction of an ionizing radiation-curable compound, the crosslinking or polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. By forming the hard coating layer in an atmosphere having an oxygen concentration of 10% by volume or less, a hard coating layer having excellent physical strength and chemical resistance can be formed.

The hard coating layer is preferably ionized radiation-atmospheric in an atmosphere having an oxygen concentration of at most 6% by volume, more preferably at most 4% by volume, particularly more preferably at most 2% by volume, and most preferably at most 1% by volume. It is formed by carrying out the crosslinking or polymerization reaction of the curable compound.

The oxygen concentration is preferably adjusted to 10% by volume or less by replacing air (nitrogen concentration: about 79% by volume, oxygen concentration: about 21% by volume) with another gas, more preferably with nitrogen (nitrogen cleaning).

The hard coat layer is preferably formed by coating the coating composition to form a hard coat layer on the transparent support.

As the solvent composition of the coating solution used to form the antiglare hard coating layer, the high refractive index layer, the hard coating layer and the low refractive index layer according to the present invention, it is preferable to use a ketone-based solvent, Can be used. In the case of mixed solvents, the content of ketone based solvents is preferably at least 10 mass%, more preferably at least 30 mass%, particularly more preferably at least 60 mass%, with respect to all solvents contained in the coating composition.

Coating solvents may contain solvents other than ketone based solvents. Examples of solvents having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point: 68.7 ° C., hereinafter abbreviated “° C.”), heptane (98.4), cyclohexane (80.7) and benzene (80.1), halogenated hydrocarbons such as dichloromethane (39.8 ), Chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5) and trichloroethylene (87.2), ethers such as diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5) and tetrahydrofuran (66), esters such as ethyl formate (54.2), methyl acetate (57.8), ethyl acetate (77.1) and isopropyl acetate (89), ketones such as acetone (56.1) and 2- Butanone (= methyl ethyl ketone, 79.6), alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4) and 1-propanol (97.2), cyano compounds such as acetonitrile (81.6) and pro Pionitrile (97.4), and carbon disulfide (46.2). Of these, ketones and esters are preferred, and ketones are more preferred. Among the ketones, 2-butanone is preferred.

Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), dioxane (101.3), dibutyl ether (142.4) Isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (= MIBK, 115.9), 1-butanol (117.7), N, N-dimethylformamide (153), N, N-dimethylacetamide (166) and dimethylsulfoxide (189). Among these, cyclohexanone and 2-methyl-4-pentanone are preferable.

Each of the coating solution for the hard coating layer and the coating solution for the low refractive index layer is prepared by diluting the components of the layer using a solvent having the composition described above. The coating solution is preferably adjusted to an appropriate concentration in consideration of the specific gravity of the constituent material and the viscosity of the coating solution, but the concentration of the coating solution is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.

The transparent support of the antireflection film of the present invention is preferably a plastic film. Examples of the polymer for forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose; representative examples thereof include TAC-TD80U and TD80UF manufactured by Fuji Photo Film), polyamide, polycarbo Nate, polyester (e.g. polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene base resin (ARTON, trade name, manufactured by JSR) and amorphous polyolefin (ZEONEX, trade name, manufactured by Nippon Zeon) Included. Among these, triacetyl cellulose, polyethylene terephthalate and polyethylene naphthalate are preferable, and triacetyl cellulose is more preferable.

Triacetyl cellulose includes monolayers or multilayers. Single layer triacetyl cellulose is produced by drum casting or band casting disclosed in JP-A-7-11055, and triacetyl cellulose comprising multiple layers is a so-called disclosed in JP-A-61-94725 and JP-B-62-43846. It is produced by a co-casting method (the term "JP-B" as used herein means "examined Japanese patent publication"). More specifically, raw flakes may be selected from halogenated hydrocarbons (eg dichloromethane), alcohols (eg methanol, ethanol, butanol), esters (eg methyl formate, methyl acetate) and ethers (eg For example, using a solvent such as dioxane, dioxolane, diethyl ether). If necessary, various additives are added thereto, such as plasticizers, ultraviolet absorbers, deterioration inhibitors, lubricants and peel accelerators. The resulting solution (named "dope") is cast on a support comprising a horizontal endless metal belt or rotating drum by dope support means (named "die"). At this time, in the case of a single layer, a single dope is cast alone, and in the case of a multilayer, high concentration cellulose ester dope and low concentration dope are co-cast on both sides thereof. The dope is dried to some extent on the support, and then the film which is given strength is peeled off from the support and the film is passed through the drying zone by various means of transport to remove the solvent.

A representative example of a solvent for dissolving triacetyl cellulose is dichloromethane. However, from the viewpoint of the global environment or the working environment, the solvent is preferably substantially free of halogenated hydrocarbons such as dichloromethane. As used herein, the term “substantially free of halogenated hydrocarbons” means that the percentage of halogenated hydrocarbons in the organic solvent is less than 5 mass% (preferably less than 2 mass%). When triacetyl cellulose dope is prepared using a solvent that is substantially free of dichloromethane and the like, a special dissolution method described below is required.

The first dissolution method, named cold dissolution method, is described below. Triacetyl cellulose is slowly added to the solvent while stirring at a temperature near room temperature (-10 to 40 ° C.). Thereafter, the mixture is cooled down to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). Cooling can be carried out in a dry ice methanol bath (-75 ° C) or in a cooled diethylene glycol solution (-30 to -20 ° C). As a result of the cooling, the mixture of triacetyl cellulose and the solvent solidifies. It is then heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.) to produce a solution in which triacetyl cellulose flows in the solvent. do. The temperature can be raised in the warm bath or by leaving the solidified mixture at room temperature.

A second method, called the hot dissolution method, is described below. Triacetyl cellulose is slowly added to the solvent while stirring at a temperature near room temperature (-10 to 40 ° C.). By adding triacetyl cellulose to a mixed solvent containing various solvents, it is preferable to swell the triacetyl cellulose for use in the present invention in advance. In the above method, it is preferable to dissolve the triacetyl cellulose up to a concentration of 30% by mass or less, but in view of drying efficiency in forming the film, the concentration is preferably higher. The mixed solution of organic solvents is then heated to 70-240 ° C. (preferably 80-220 ° C., more preferably 100-200 ° C., most preferably 100-190 ° C.) under a pressure of 0.2-30 MPa. . The heated solution cannot be coated on its own and must be cooled to a temperature below the lowest boiling point of the solvent used. In this case, the solution is gradually cooled to −10 to 50 ° C. and returned to atmospheric pressure. Cooling may be carried out by leaving the high pressure hot container or line containing the triacetyl cellulose solution only at room temperature, or preferably the apparatus may be cooled using a cooling medium such as cooling water. Cellulose acetate films substantially free of halogenated hydrocarbons such as dichloromethane, and methods for their preparation are described in JIII Journal of Technical Disclosure (2001-1745, issued March 15, 2001, hereinafter "Kokai Giho 2001-1745"). (Abbreviated as ")".

When using the antireflective film of the present invention for a liquid display device, the antireflective film is disposed on the outermost surface of the display, for example by providing an adhesive layer on one surface. In the case where the transparent support is triacetyl cellulose, since triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate, it is preferable to use the antireflection film of the present invention for the protective film in view of cost. Do.

When the antireflective film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one surface or used for a protective film of a polarizing plate, it mainly comprises a fluorine-containing polymer formed on a transparent support. It is preferable to saponify the outermost layer to obtain satisfactory adhesion. The saponification treatment is carried out by known methods, for example by immersing the film in an alkaline solution for a suitable time. After immersion in the alkaline solution, it is preferable to prevent the alkali component from remaining in the film by washing the film entirely with water or by dipping in a dilute acid for neutralizing the alkyl component.

By the saponification treatment, the surface of the transparent support is hydrophilized on the opposite side of the surface having the outermost layer.

The hydrophilized surface is particularly effective for imparting adhesion to a deflection film mainly comprising polyvinyl alcohol. In addition, the hydrophilized surface hardly adheres to dust in the air, and when combined with the deflection film, the dust hardly penetrates into the space between the deflection film and the antireflection film, so that a dot derect due to the dust is prevented. Can be effectively prevented.

The saponification treatment is preferably carried out such that the surface of the transparent support on the opposite side of the surface with the outermost layer has a contact angle with water of 40 ° or less, preferably 30 ° or less, more preferably 20 ° or less.

The alkali saponification treatment method can be specifically selected from the following two methods (1) and (2). Method (1) is advantageous in that this treatment can be carried out by the same steps as for general purpose triacetyl cellulose films, but since the antireflective film surface is also saponified, the surface is alkali hydrolyzed and the film Or deterioration of the solution, or if a solution for the saponification treatment remains, this causes a problem of staining. If this is the case, method (2) is advantageous despite the need for a specific step for the treatment.

(1) After the formation of the antireflection layer on the transparent support, the back side of the film is saponified by immersing the film in the alkyl solution one or more times.

(2) before or after forming the antireflective layer on the transparent support, an alkaline solution is coated on the surface on the opposite side of the surface on which the antireflective film is formed, and then the film is heated, washed and / or neutralized with water, Only saponify the back side of the film.

The antireflection film of the present invention may be formed by the following method, but the present invention is not limited to this method.

A coating solution containing the components for forming each layer is prepared. Immersion coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method or extrusion coating method (see US Patent No. 2,681,294) The coating solution for forming the hard coat layer is then coated onto the transparent support, which is then heated and dried. Of these coating methods, the microgravure coating method is preferable. The formed coating is irradiated with light or heated to polymerize monomers to form an antiglare hard coat layer and to cure the polymer to form a hard coat layer.

If desired, the hard coat layer may consist of multiple layers, in which case the smooth hard coat layer may be coated and cured in the same manner before the coating of the antiglare hard coat layer.

Thereafter, the coating solution for forming the low refractive index layer is coated on the hard coating layer in the same manner and irradiated or heated with light to form the low refractive index layer. In this way, the antireflection film of the present invention is obtained.

The microgravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm, and having a gravure pattern coated on the entire circumference thereof in a direction opposite to the transport direction of the support. By rotating under the support and at the same time scraping the excess coating solution from the surface of the gravure roll by a doctor blade, a certain amount of coating solution is transported, leaving the upper surface of the support in the free state, while It is a coating method characterized in that the coating on the surface. The roll forming transparent support is continuously spread, and on one surface of the spread support, at least one of the low refractive index layer and the hard coating layer containing the fluorine-containing polymer may be coated by the microgravure coating method.

With respect to the coating conditions by the microgravure coating method, the number of lines in the gravure pattern coated on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern Is preferably 1 to 600 µm, more preferably 5 to 200 µm, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the support conveying speed is preferably 0.5 to 100 m / min, more preferably 1 to 50 m / min.

The haze value of the antireflection film of the present invention thus formed is 3 to 70%, preferably 4 to 60%, and an average reflectance at 450 to 650 nm is 3.0% or less, preferably 2.5% or less.

The antireflection films of the present invention have haze values and average reflectances in the above ranges, respectively, so that excellent antiglare and antireflection properties can be obtained without deterioration of the transmitted image.

A polarizing plate is mainly comprised by two protective films which sandwich a polarizing film and a polarizing film between both surfaces. The antireflective film of the present invention is preferably used for one or more sheets of two protective films sandwiching the polarizing film between both sides. When the antireflective film of the present invention is simultaneously provided as a protective film, the production cost of the polarizing plate can be reduced. In addition, when the antireflective film of the present invention is used as a polarizing plate, an outermost layer which is protected from reflection of external light and the like and is excellent in scratch resistance, antifouling properties may be produced.

As the polarizing film, a known polarizing film or a polarizing film whose absorption axis of the polarizing film is cut out from a long polarizing film that is not perpendicular or parallel to the longitudinal direction may be used. An elongate polarizing film in which the absorption axis of the polarizing film is not perpendicular or parallel to the longitudinal direction is produced by the following method.

That is, the polarizing film is obtained by stretching a polymer film continuously supplied under the application of tension while supporting both edges of the film with the supporting means, and the film has a scratch in the cross direction of the film of 1.1 to 20.0 times or more. It can be produced by the method, the difference in the movement speed of the longitudinal support means between the two edges of the film is 3% or less, with both edges of the film supported, the direction of movement of the film, both edges of the film In the step of supporting the angle formed by the moving direction of the film at the exit and the substantially stretching direction of the film is bent to be inclined at 20 to 70 °. In particular, a stretching method that provides an inclination angle of 45 ° is preferable in terms of productivity.

The scratching method of the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

The antireflective film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescent display (ELD) and a cathode ray tube display device (CRT). Since the antireflection film of the present invention has a transparent support, the film is used by adhering the transparent support side to the image display surface of the image display apparatus.

In the case of using the antireflective film of the present invention as a protective film on one surface of the polarizing film, the antireflective film is a twisted nematic (TN) method, a super twisted nematic (STN) method, a vertical orientation. (vertical alignment, VA), in-plane switching (IPS), or optically compensated bend cell (OCB) methods, such as those preferably used for transmission, refractive, or transflective liquid crystal display devices. Can be.

In the VA-type liquid crystal cell, (1) VA in a narrow sense, in which a bar-type liquid crystal molecule is oriented substantially vertically when no voltage is applied and the molecule is oriented substantially horizontally when a voltage is applied. -Type liquid crystal cell (see JP-A-2- 176625), (2) multi-domain VA-type (MVA-type) liquid crystal cell for expanding the viewing angle ( SID97, Digest of Tech.Papers (preliminary), 28, 845 (1997)), (3) the manner in which the bar-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and in which the molecules are oriented in a twisted multi-zone manner when voltage is applied ( n-ASM type liquid crystal cell (see Nippon Ekisho Toron Kai (Japan Liquid Crystal Workshop ) (preliminary), 58-59 (1998))) and (4) SURVIVAL-type liquid crystal cell (presented by LCD International '98). Is included).

The OCB-type liquid crystal cell is a liquid crystal display device using a bend alignment type liquid crystal cell in which bar-shaped liquid crystal molecules are aligned (symmetrically) in a substantially reverse direction between upper and lower portions of the liquid crystal cell. This is disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the bar-shaped liquid crystal molecules are symmetrically oriented at the top and bottom of the liquid crystal cell, the bend array-type liquid crystal cell has a self-optical compensation function. Thus, the liquid crystal system is also called OCB (optically compensatory bend) liquid crystal system. The bend alignment-type liquid crystal display device is advantageous in that the response speed is fast.

In the ECB-type liquid crystal cell, when no voltage is applied, the bar-shaped liquid crystal molecules are substantially horizontally aligned. This is most commonly used as a color TFT liquid crystal display device and described in numerous documents such as EL, PDP, LCD Display, Toray Research Center (2001).

 In particular, in the TN-type or IPS-type liquid crystal display device, when an optical correction film having a magnification effect of the viewing angle is used, the front and rear surfaces of the two protective films of the polarizer, For the protective film on the opposite surface of the antireflection film of the present invention as described, a polarizing plate having a thickness of one polarizing plate and having an antireflection effect and a viewing angle enlargement effect can be obtained, which is preferable.

The invention will be described in more detail below with reference to the examples, but the invention is not limited thereto. Unless otherwise indicated, "parts" and "%" are by mass.

(Synthesis of Perfluoroolefin Copolymer (1))

Perfluoroolefin Copolymers (1)

40 ml ethyl acetate, 14.7 g hydroxyethyl vinyl ether and 0.55 g dilauryl peroxide were charged into a stainless-steel autoclave with an internal volume of 100 ml and equipped with a stirrer. The interior of the system was degassed and washed with nitrogen gas. Thereafter, 25 g of hexafluoropropylene (HFP) was further introduced into the autoclave and the temperature was raised to 65 ° C. The pressure was 5.4 kg / cm ² when the internal temperature of the autoclave reached 65 ° C. The reaction was continued for 8 hours while maintaining the temperature and when the pressure reached 3.2 kg / cm ² , heating was stopped and the system was left to cool. When the internal temperature was lowered to room temperature, the unreacted monomer was removed, the autoclave was opened, and the reaction solution was taken. The resulting reaction solution was charged into a very excess of hexane, the solvent was removed by decantation and the precipitated polymer was taken. The polymer was dissolved in a small amount of ethyl acetate and reprecipitation from hexane was performed twice to completely remove residual monomer. After drying, 28 g of polymer was obtained. Thereafter, 20 g of the resulting polymer was dissolved in 100 ml N, N-dimethylacetamide, 11.4 g chloride acrylate was added dropwise under ice cooling, and the resulting solution was stirred at room temperature for 10 hours. After adding ethyl acetate, the reaction solution was washed with water and the organic layer was extracted and concentrated. The resulting polymer was reprecipitated with hexane to give 19 g of perfluoroolefin copolymer (1). The refractive index of the resulting polymer was 1.421.

(Preparation of sol solution a)

In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103 ™, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts of diiso Propoxyaluminum ethyl acetate was added and mixed, to which 30 parts of ion-exchanged water was added and the resulting mixture was reacted at 60 ° C. for 4 hours and then cooled to room temperature to obtain a sol solution a. Was 1,600 and a component having a molecular weight of 1,000 to 20,000 accounted for 100% of the oligomeric components. Furthermore, gas chromatography analysis showed that no raw acryloyloxypropyltrimethoxysilane remained at all.

(Preparation of sol solution b)

The sol solution b was obtained in the same manner as the sol component a except that 6 parts of acetylacetone were added after the reaction and cooling to room temperature.

(Preparation of Coating Solution A for Antiglare Hard Coating Layer)

Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (15 g) and 24 g trimethylolpropane EO-added triacrylate (M-309 , Osaka Yuki Kagaku Co., Ltd.) were mixed and the resulting mixture was diluted with 10 g of methyl isobutyl ketone and 6 g of methyl ethyl ketone. 2 g of polymerization initiator Irgacure 184 (manufactured by Ciba Fine Chemicals) was added thereto and mixed with stirring. The resulting solution was coated and UV-cured and the resulting film had a refractive index of 1.53.

To this solution, a 30% methyl isobutyl ketone dispersion solution of reinforced and crosslinked polystyrene particles (SXS-350H, trade name, manufactured by Soken Kagaku KK) sorted to an average particle size of 3.5 μm was applied for 20 minutes at 10,000 rpm in a polytron dispersion. 10 g of the dispersion solution obtained by dispersion during A 30% methyl isobutyl ketone dispersion solution of reinforced and crosslinked polystyrene particles (SXS-500H, trade name, manufactured by Soken Kagaku KK) classified to an average particle size of 5 μm was then dispersed for 30 minutes at 10,000 rpm in a polytron dispersion. 13 g of the dispersion solution obtained by adding was added. Finally, the solution was completed by adding 1.2 g of the sol component a of the organosilane.

 The obtained mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution A for an antiglare hard coat layer.

(Preparation of Coating Solution B for Antiglare Hard Coating Layer)

Commercially available zirconia-containing UV curable hard coating solution (DESOLITE Z7404, manufactured by JSR, solids concentration: about 61%, ZrO ₂ content in solids content: about 70%, with polymerizable monomer and polymerization initiator) (285 g ) And 85 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were mixed and the resulting mixture was mixed with 60 g methyl isobutyl ketone and 17 g. g diluted with methyl ethyl ketone. 28 g of the silane coupling agent KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto and mixed with stirring. The resulting solution was coated and UV-cured and the resulting coating film had a refractive index of 1.61.

To this solution, 30% methyl isobutyl ketone dispersion solution of reinforced and crosslinked PMMA particles (MXS-300, trade name, manufactured by Soken Kagaku KK) classified to an average particle size of 3.0 μm was added at 10,000 rpm in a polytron dispersion. 35 g of the dispersion solution obtained by dispersion for minutes were added. A 30% methyl ethyl ketone dispersion solution of silica particles (SEAHOSTA KE-P150, trade name, manufactured by Nippon Shokubai Co., Ltd.) with an average particle size of 1.5 μm was then dispersed in a polytron dispersion at 10,000 rpm for 30 minutes. The solution was completed by adding 90 g of the dispersion solution obtained by mixing and mixing with stirring.

 The resulting mixed solution was filtered through a filter made of polypropylene with a pore size of 30 μm to prepare coating solution B for an antiglare hard coat layer.

(Preparation of coating solution C for antiglare hard coat layer)

Reinforced and highly crosslinked PMMA, which is classified into an average particle size of 1.5 μm instead of silica particles having an average particle size of 1.5 μm in the preparation of coating solution C for an antiglare hard coating layer, and coating solution B for an antiglare hard coating layer Addition amount except that 130 g of 30% methyl ethyl ketone dispersion solution of particles (MXS-150H, trade name, crosslinker: ethylene glycol dimethacrylate, amount of crosslinker: 30%, manufactured by Soken Kagaku KK) is used It was prepared in the same manner as coating solution B.

(Preparation of Coating Solution D for Antiglare Hard Coating Layer)

The coating solution D for the antiglare hard coating layer is the same as the coating solution B, except that 0.1 g of fluorine-based polymer R-1 is added in the preparation of the coating solution B for the antiglare hard coating layer. It was prepared by the method.

(Preparation of Coating Solution A for Low Refractive Index Layer)

To 18 g of a thermally crosslinkable fluorine-containing polymer (JN-7228, solid concentration: 6%, manufactured by JSR) having a refractive index of 1.42, 0.4 g of a sol solution a, 2 g of methyl ethyl ketone and 0.6 g of cyclohexanone were added. Added and stirred. The resulting solution was filtered through a filter made of polypropylene with a pore size of 1 μm to prepare coating solution A for the low refractive index layer.

(Preparation of Coating Solution B for Low Refractive Index Layer)

Thermally crosslinkable fluorine-containing polymer with refractive index 1.42 (JN-7228, solid concentration: 6%, manufactured by JSR) (15 g), 1.4 g silica sol (silica, MEK-ST, average particle size: 15 nm, solid Concentration: 30%, manufactured by Nissan Chemicals Industries, Ltd.), 0.4 g of sol solution a, 3 g of ethyl ethyl ketone and 0.6 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a pore size of 1 μm to prepare coating solution B for the low refractive index layer.

(Preparation of Coating Solution C for Low Refractive Index Layer)

Thermally crosslinkable fluorine-containing polymer with refractive index 1.42 (JN-7228, solid concentration: 6%, manufactured by JSR) (15 g), 1.4 g silica sol (silica, MEK-ST with different particle sizes, average particle size: 45 nm, solid concentration: 30%, manufactured by Nissan Chemicals Industries, Ltd.), sol solution a of 0.4 g of organosilane, 3 g of methyl ethyl ketone and 0.6 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a pore size of 1 μm to prepare coating solution C for low refractive index layer.

(Preparation of Coating Solution D for Low Refractive Index Layer)

Perfluoroolefin copolymer (1) (15.2 g), 1.4 g silica sol (silica, MEK-ST with different particle sizes, average particle size: 45 nm, solids concentration: 30%, from Nissan Chemicals Industries, Ltd. 0.3 g of reactive silicon X-22-164B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7.3 g of sol solution a, 0.76 g of photopolymerization reaction initiator (Irgacure 907 (trade name), Ciba Geigy Co. Ltd.), 301 g of methyl ethyl ketone and 9.0 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a pore size of 5 μm to prepare coating solution D for the low refractive index layer.

Example 1

(1) formation of an antiglare hard coating layer

Dr. coating solution A for anti-glare hard coating layer prepared above by spreading 80 탆 -thick triacetyl cellulose film (TAC-TD80UL, manufactured by Fuji Photo Film Co., Ltd.) in the form of a roll Gravure roll at 30 rpm using a doctor blade and a microgravure roll with a diameter of 50 mm with a number of lines of 180 lines / inch and a gravure pattern of 40 μm deep Coating at rotation and transfer speed of 10 m / min. Thereafter, the coating solution was dried at 60 ° C. for 150 seconds, and then, under nitrogen washing, an irradiance of 400 mW / cm ² using a 160 W / cm air-cooled metal halide lamp (manufactured by I-Graphics KK) and The coating layer was cured by irradiating with ultraviolet radiation at a dose of 250 mJ / cm ² to form an antiglare hard coating layer having a 4.3 μm thickness. Thereafter, the film was taken.

(2) formation of a low refractive index layer

The triacetyl cellulose film coated with an antiglare hard coating layer thereon was again spread, and the coating solution C for the low refractive index layer prepared above had a doctor blade and a gravure pattern having a line number of 180 lines / inch and a depth of 40 μm. Using a microgravure roll with a diameter of 50 mm, it was coated on at a gravure roll rotation of 30 rpm and a feed speed of 15 m / min. Thereafter, the coating solution was dried at 140 ° C. for 8 minutes and then under a nitrogen wash, a roughness of 400 mW / cm ² using a 240 W / cm air cooled metal halide lamp (manufactured by I-Graphics KK) and Ultraviolet rays were irradiated at a dose of 900 mJ / cm ² to form a low refractive index layer having a thickness of 100 nm. Thereafter, the film was taken.

(Saponification of antireflection film)

After the film formation, the sample 1 was subjected to the following treatment.

A 1.5 N aqueous sodium hydroxide solution was prepared and maintained at 55 ° C. In addition, 0.01 N dilute aqueous sulfuric acid solution was prepared. The obtained antireflection film was immersed in the prepared aqueous sodium hydroxide solution for 2 minutes and then immersed in water to thoroughly wash the aqueous sodium hydroxide solution. Subsequently, the film was immersed in the prepared diluted sulfuric acid aqueous solution for 1 minute and then immersed in water to thoroughly wash the prepared diluted sulfuric acid aqueous solution. Finally, the sample was completely dried at 120 ° C.

In this way, a saponified antireflection film was produced. The film is named as Example Sample 1

(Evaluation of antireflection film)

The obtained film was evaluated according to the following items. The results are shown in Table 1.

(1) average reflectance

The spectral reflectance at an incident angle of 5 ° in the wavelength region of 380 nm to 780 nm was measured using a spectrometer (manufactured by JASCO Corporation). For the results, the integrated sphere average reflectance at 450 nm to 650 nm was used.

(2) Evaluation of Scratch Resistance to Steel Wool

Friction tests were performed using a friction tester under the following conditions:

Evaluation environmental conditions: 25 ℃, 60% RH

Friction material:

Steel wool (Grade No. 0000, manufactured by Nippon Steel Wool K.K.) was wrapped around the friction tip (1 cm x 1 cm) of the tester in contact with the sample, secured with a band and supported by it.

Travel Distance (One Direction): 13 cm

Friction Speed: 13 cm / sec

Load: 500 g / cm 2

Tip contact area: 1 cm x 1 cm

Friction: 10 round trips

The oily black ink was coated on the back side of the rubbing sample and the reflected light was visually observed. Scratchability of the friction site was evaluated according to the following criteria:

매우 주의깊게 관측시에도 스크래치가 전혀 관측되지 않음.

No scratches were observed even with very careful observation.

매우 주위깊게 관측시 희미한 스크래치가 약간 관측됨.

Very faint scratches are observed when observed very closely.

희미한 스크래치가 관측됨.

Faint scratches are observed.

중간 정도의 스크래치가 관측됨.

Medium scratches are observed.

스크래치가 한눈에 관측됨.

Scratch is observed at a glance.

(3) Evaluation of Scratch Resistance to Bencott

Friction tests were performed using a friction tester under the following conditions:

Evaluation environmental conditions: 25 ℃, 60% RH

Friction material:

Bencote (manufactured by Ozo Sangyo K.K.) was wrapped around the friction tip (1 cm x 1 cm) of the tester, in contact with the sample, secured with a band and supported by it.

Travel Distance (One Direction): 13 cm

Friction Speed: 13 cm / sec

Load: 200 g / cm 2

Tip contact area: 1 cm x 1 cm

Friction: 10 round trips

The oily black ink was coated on the back side of the rubbing sample and the reflected light was visually observed. Scratchability of the friction site was evaluated according to the following criteria:

매우 주의깊게 관측시에도 스크래치가 전혀 관측되지 않음.

No scratches were observed even with very careful observation.

매우 주위깊게 관측시 희미한 스크래치가 약간 관측됨.

Very faint scratches are observed when observed very closely.

희미한 스크래치가 관측됨.

Faint scratches are observed.

중간 정도의 스크래치가 관측됨.

Medium scratches are observed.

스크래치가 한눈에 관측됨.

Scratch is observed at a glance.

(4) effect of scattered light profile

Using an Autogoniophotometer model GP-5 from Murakami Color Research Laboratory, the film was placed perpendicular to the incident light and the scattering profiles were measured on all orientations. From the obtained profile, the scattered light intensity at 30 ° was determined based on the brightness at the exit angle of 0 °.

[Samples 2 to 90 of Example 1 and Samples 1 to 19 of Comparative Example 1]

Sample 1 of Example 1, coating solution for antiglare hard coating layer (B, C, D) or coating solution for low refractive index layer (A, B, D to Z, α to μ) is shown in Tables 1 to 4 The sample was prepared and evaluated in the same manner as in Example 1, except that it was charged as follows.

Here, coating solutions F to Z and α to μ for the low refractive index layer are coated for the low refractive index layer, except that the coated amount thereof and the average particle size of the silica fine particles are changed as shown in the following table. Coated in the same manner as solution C or D.

The thickness of the antiglare hard coat layer after drying was 4.3 μm for Coating Solution A and 3.4 μm for Coating Solutions B, C and D.

The results in Tables 1-4 indicate the following.

When silica fine particles having the average particle size described above in the present invention are included in the low refractive index layer, excellent scratch resistance can be obtained despite being a low refractive index layer comprising a fluorine-containing polymer and an antireflection film having a low reflectance is obtained. Can be obtained.

When a combination of silica fine particles having a small particle size is used, scratch resistance is further improved.

Furthermore, when the silica fine particles are replaced with hollow silica fine particles, the refractive index of the silica fine particles themselves is reduced, so that the reflectance can be further reduced and a good antireflection film can be obtained.

For samples 25 to 48 and 79 to 84 of Example 1, a high-speed coated, good coating surface on the support at a transport rate of 20 m / min using coating solution D instead of coating solution B for an antiglare hard coat layer State was obtained and performance was also good.

The sol solution b of organosilane was used instead of the sol d solution a used in the coating solution for the low refractive index layer, which improved aging stability and increased suitability in continuous coating.

Furthermore, 10 g of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added to the coating solution D for the low refractive index layer to add the coating solution in the same manner. When coated, scratch resistance was significantly improved.

Example 2

(Preparation of Coating Solution for Hard Coating Layer)

To 315.0 g of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone dispersion of silica fine particles (MEK-ST, solid concentration: 30) Mass%, 450.0 g of Nissan Chemicals Industries, Ltd.), 15.0 g of methyl ethyl ketone, 220.0 g of cyclohexanone, and 16.0 g of a photoinitiator (Irgacure 907, manufactured by Nippon Ciba Geigy) were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a 0.4 μm pore size to prepare a coating solution for the hard coat layer.

(Preparation of Titanium Dioxide Fine Particle Dispersion Solution)

The titanium dioxide fine particles used were cobalt and titanium dioxide fine particles (MPT-129, manufactured by Ishihara Sangyo Kaisha, Ltd.) which were surface treated with aluminum hydroxide and zirconium hydroxide.

To 257.1 g of the particles, 38.6 g of the dispersant shown below and 704.3 g of cyclohexanone were added and dispersed in Dyno-mill to prepare a titanium dioxide dispersion solution having a mass average size of 70 nm:

(Preparation of Coating Solution for Medium Refractive Index Layer)

To 88.9 g of the titanium dioxide dispersion solution prepared above, 58.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerization initiator (Irgacure 907), a photosensitive agent (KAYACURE DETX, Nippon 1.1 g of Kayaku Co., Ltd.), 482.4 g of methyl ethyl ketone and 1,869.8 g of cyclohexanone were added and stirred. After complete stirring, the resulting solution was filtered through a filter made of polypropylene with a 0.4 μm pore size to prepare a coating solution for the medium refractive index layer.

(Preparation of coating solution for high refractive index layer)

47.9 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) in 586.8 g of the titanium dioxide dispersion solution prepared above, a photopolymerization initiator (Irgacure 907, 4.0 g of Nippon Ciba, manufactured by Geigy, 1.1 g of a photosensitizer (KAYACURE DETX, manufactured by Nippon Kayaku Co., Ltd.), 455.8 g of methyl ethyl ketone, and 1,427.8 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a 0.4 μm pore size to prepare a coating solution for the high refractive index layer.

(Preparation of coating solution i for low refractive index layer)

10.8 g of thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (product having a different solvent from JN-7228, solid concentration: 10%, manufactured by JSR), 0.4 g of a sol solution, 2 g of methyl ethyl ketone, and 0.6 cyclohexanone g was added and stirred. The resulting solution was filtered through a filter made of polypropylene with a pore size of 1 μm to prepare a coating solution i for the low refractive index layer.

(Preparation of coating solution ii for low refractive index layer)

Silica sol (silica, MEK-ST, average particle size: 15 nm, in 9 g of a thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (product having a different solvent than JN-7228, solid concentration: 10%, manufactured by JSR) Solid concentration: 30%, 1.4 g of Nissan Chemicals Industries, Ltd.), 0.4 g of sol solution, 3 g of methyl isobutyl ketone, and 0.6 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a 1 μm pore size to prepare a coating solution ii for the low refractive index layer.

(Preparation of coating solution iii for low refractive index layer)

Silica sol (silica, MEK-ST with different particle sizes, average particle size) to 9 g of a thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (product having a different solvent from JN-7228, solid concentration: 10%, manufactured by JSR) : 45 nm, solid concentration: 30%, 1.4 g from Nissan Chemicals Industries, Ltd.), 0.4 g of a sol solution of organosilane, 3 g of methyl isobutyl ketone, and 0.6 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a 1 μm pore size to prepare a coating solution iii for the low refractive index layer.

(Preparation of coating solution iv for low refractive index layer)

Perfluoroolefin copolymer (1) (15.2 g), silica sol (silica, MEK-ST having different particle sizes, average particle size: 45 nm, solid concentration: 30%, manufactured by Nissan Chemicals Industries, Ltd.) 1.4 g, reactive silicone X-22-164B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 g, sol solution a 7.3 g, photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba Geigy) 0.76 g, 301 g of methyl isobutyl ketone and 9.0 g of cyclohexanone were added and stirred. The resulting solution was filtered through a filter made of polypropylene with a 5 μm pore size to prepare coating solution iv for the low refractive index layer.

(Manufacture of antireflection film)

The coating solution for the hard coat layer was coated on an 80 μm thick triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) using a gravure coater, and dried at 100 ° C. Then, using a metal halide lamp (160 I / Graphics KK), which is air cooled under nitrogen cleaning, in which the concentration of oxygen in the atmosphere is reduced to 1.0 vol% or less, an illuminance of 400 mW / cm ² and Ultraviolet rays were irradiated here at a dose of 300 mJ / cm ^2, whereby the coating layer was cured to form a hard coating layer having a thickness of 3.5 μm.

On the hard coat layer, the coating solution for the medium refractive index layer was coated using a gravure coater and dried at 100 ° C. Thereafter, using a 240 W / cm air cooled metal halide lamp (manufactured by I-Graphics KK) under nitrogen scrubbing to reduce the concentration of oxygen in the atmosphere to 1.0 vol% or less, an illuminance of 550 mW / cm ² and Ultraviolet rays were irradiated here at a dose of 600 mJ / cm ^2, whereby the coating layer was cured to form a medium refractive index layer (refractive index: 1.65, film thickness: 67 nm).

On the above medium refractive index layer, the coating solution for the high refractive index layer was coated using a gravure coater and dried at 100 ° C. Thereafter, using a 240 W / cm air cooled metal halide lamp (manufactured by I-Graphics KK) under nitrogen scrubbing to reduce the concentration of oxygen in the atmosphere to 1.0 vol% or less, an illuminance of 550 mW / cm ² and Ultraviolet rays were irradiated here at a dose of 600 mJ / cm ^2, whereby the coating layer was cured to form a high refractive index layer (refractive index: 1.93, film thickness: 107 nm).

On the high refractive index layer, the coating solution iv for the high refractive index layer was coated using a gravure coater and dried at 80 ° C. Afterwards, using a metal halide lamp of 160 W / cm air cooled under nitrogen scrubbing to reduce the concentration of oxygen in the atmosphere to 1.0 vol% or less, an illuminance of 550 mW / cm ² and Ultraviolet rays were irradiated here at a dose of 600 mJ / cm ² , thereby forming a low refractive index layer (refractive index: 1.43, film thickness: 86 nm). In this way, the antireflective film sample 1 of Example 2 of the present invention was prepared.

(Evaluation of antireflection film)

The obtained film was evaluated for the above-mentioned items. The results are shown in Table 5.

[Samples 2 to 30 of Example 2 and Samples 1 to 7 of Comparative Example 2]

These samples were prepared and evaluated in the same manner as Sample 1 of Example 2, except that the coating solution for the low refractive index layer (i to iii, v to xxxvii) of Sample 1 of Example 2 in Table 5 was changed. .

The results are shown in Tables 5 and 6.

The coating solutions v to xxxvii for the low refractive index layer are the same except for changing the thickness, average particle size of silica fine particles and amount of coated silica fine particles as shown in the table below.

The results in Tables 5 and 6 show the following.

When silica fine particles having the above average particle size are included in the low refractive index layer in the present invention, excellent scratch resistance can be obtained despite being a low refractive index layer including a fluorine-containing polymer and an antireflection film having excellent antireflection performance. Can be obtained.

When a combination of silica fine particles having a small particle size is used, scratch resistance is further improved.

Furthermore, when the silica fine particles are replaced with hollow silica fine particles, the refractive index of the silica fine particles themselves is reduced, so that the reflectance can be further reduced and an antireflection film with improved antireflection performance can be obtained.

Example 3

The PVA film was immersed in an aqueous solution containing 2.0 g / liter of iodine and 4.0 g / liter of potassium iodide at 25 ° C. for 240 seconds and further in an aqueous solution containing 10 g / liter of boric acid at 25 ° C. for 60 seconds. It was immersed. The film was then introduced into a tenter stretching machine of the type shown in Figure 2 of JP-A-2002-86554 and stretched 5.3 times. The tender was then bent as shown in FIG. 2 with respect to the stretching direction and then the width was kept constant. The film was dried at 80 ° C. in air and removed in a tenter. The difference in transport speed between the left and right tenter clips was less than 0.05% and the angle created by the centerline of the introduced film and the film centerline delivered to the next step was 46 °. Here, | L1-L2 | was 0.7 m, W was 0.7 m, and the relationship of | L1-L2 | = W was established. The substantial stretching direction Ax-Cx at the tenter outlet was tilted 45 ° with respect to the centerline 22 of the film to be transferred to the next step. From the tenter exit. No wrinkles and deformations of the film were observed.

Using 3% aqueous PVA solution (PVA-117H, manufactured by Kuraray Co., Ltd.) as an adhesive, the film was attached to saponified Fujitac (cellulose triacetate, decay value: 3.0 nm) manufactured by Fuji Photo Film Co., Ltd. The bonded film was heated at 80 ° C. to obtain a polarizing film having an effective width of 650 nm. The absorption axis direction of the obtained polarizing plate was tilted at 45 degrees with respect to the longitudinal direction. The transmittance at 550 nm of the polarizing plate was 43.7%, and the degree of polarization was 99.97%. Further, the polarizing plate was cut to a size of 310 x 233 mm as in FIG. 2, and as a result, a polarizing plate having an absorption axis tilted at 45 ° with respect to the side surface was obtained with an area efficiency of 91.5%.

Subsequently, Example samples 1 and 2 (saponification) were attached to the polarizing plate to prepare polarizing plates having antiglare and antireflection films. Using this polarizing plate, the liquid crystal display device which has an antiglare and an antireflection layer in the outermost layer was manufactured. As a result, no reflection of external light occurred and excellent contrast was obtained. In addition, thanks to the anti-glare characteristic, the reflected image disappears, thereby ensuring high visibility.

Example 4

On both sides of the polarizer prepared by absorbing iodine in polyvinyl alcohol and stretching the film, it was immersed in 1.5N aqueous NaOH solution at 55 ° C. for 2 minutes, neutralized and washed with water, and the back side of the film was saponified at 80 μm-thickness. EXAMPLES The triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) of Sample 1 was attached and protected therewith to prepare a polarizing plate. The obtained polarizing plate is a liquid crystal display device of a notebook-type personal computer having a transparent TN liquid crystal display device (having D-BEF manufactured by Sumitomo 3M, which is a polarization separating film having a polarization selective layer between a halo and a liquid crystal cell). In exchange with the polarizing plate on the viewing side, the antireflection film surface was brought to the outermost surface. As a result, the reflection of the background was extremely reduced and a high quality display device was obtained.

Example 5

A viewing angle magnifying film having an optical correction layer in which the disc plane of the discotic structural unit is inclined with respect to the transparent support plane and the angle made by the disc plane and the transparent support plane of the discotic structural unit varies in the depth direction of the optically anisotropic layer. (Wide View Film SA-12B, manufactured by Fuji Photo Film Co., Ltd.), the protective film on the liquid crystal cell side of the polarizing plate attached to Example Samples 1 and 2 and positioned on the viewing side of the transparent TN liquid crystal cell, And also as a protective film on the liquid crystal cell side of the polarizing plate located on the backlight side. As a result, the contrast in the bright room was very high, the viewing angles in the horizontal and vertical directions were also very wide and the visibility was remarkably good. Thus, a liquid crystal display device having high picture quality was obtained. Samples 25-72 and 79-90 (using the anti-glare hard coating solutions B and C) of Example 1 had a scattering luminous intensity of 0.06% to a luminous intensity at exit angle 0 ° and using such a sample In the case, due to their light scattering properties, the viewing angle in the downward direction and yellow tinting in the horizontal direction were particularly improved and a very good liquid crystal display device was obtained. For comparative films made in the same manner as Samples 25-48 and 79-84 of Example 1, except that the crosslinked PMMA particles and silica particles were removed from the antiglare hard coat solution B, at an exit angle of 0 ° The scattering luminous intensity of 30 ° with respect to the luminous intensity was substantially 0%, and there was no effect of increasing the viewing angle in the downward direction and improving tinting in yellow.

Example 6

Through the pressure-sensitive adhesive, Example Samples 1 and 2 were attached to the glass plate on the surface of the organic EL display device, and as a result, the display device with the suppressed reflection on the glass surface was obtained.

Example 7

EXAMPLES Samples 1 and 2 were used to prepare polarizing plates with antireflective films on the surface, and to attach λ / 4 plates to the opposite surface of the surface with antireflective films of the polarizing plates. The polarizing plate was attached to the glass plate on the surface of the organic EL display device, and as a result, the surface reflection and the reflection from the inside of the surface glass were blocked to obtain a display device having high visibility.

The antireflective film of the present invention has sufficiently high antireflective properties and at the same time ensures good scratch resistance. The display device equipped with the antireflective film of the present invention and the display device equipped with the polarizing plate using the antireflective film of the present invention are preferable because the reflection of external light and the reflection of the background are reduced and very high visibility.

Claims (14)

Transparent support; And a low refractive index layer comprising a fluorine-containing polymer as the outermost layer, The low refractive index layer comprises one or more inorganic fine particles having an average particle size of 30 to 100% of the low refractive index layer thickness, The inorganic particles are silica fine particles, At least one silica fine particle of the low refractive index layer is a hollow silica fine particle having a refractive index of 1.17 to 1.40. The antireflection film of claim 1 having one or more hard coating layers between the transparent support and the low refractive index layer. delete The antireflection film of claim 1 wherein the low refractive index layer further comprises one or more silica fine particles having a particle size of less than 25% of the thickness of the low refractive index layer. delete 2. The fluorine-containing polymer according to claim 1, wherein the fluorine-containing polymer is a copolymer (P) having a main chain composed solely of carbon atoms, the copolymer comprising: a fluorine-containing vinyl monomer polymerization unit; And a polymerization unit having a (meth) acryloyl group in the side chain. The antireflection film according to claim 6, wherein the copolymer (P) is represented by the following general formula (1):   [Formula 1]

[Wherein L represents a linking group having 1 to 10 carbon atoms, m represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents an arbitrary vinyl monomer polymerization unit and a single component or a plurality of components Wherein x, y and z represent mole percent of each component and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70 and O ≦ z ≦ 65. 3. The method of claim 2, wherein the at least one hard coating layer is a light-diffusion layer, the light-diffusion layer at a light intensity at an exit angle of 0 ° in the scattered light profile by a goniophotometer. It has a scattering luminous intensity in 30 degrees which is 0.01 to 0.2% with respect to. The antireflective film of claim 1, comprising at least one high refractive index layer between the transparent support and the low refractive index layer, wherein the high refractive index layer has a refractive index of 1.55 to 2.40 and is mainly a layer comprising Dioxide; And at least one element selected from cobalt, aluminum and zirconium. The antireflective film of claim 1, wherein the low refractive index layer has a refractive index of 1.20 to 1.49. A polarizing plate comprising two protective films of a polarizer and a polarizer, wherein one of the two protective films of the polarizer is an antireflection film according to claim 1. 12. The polarizing plate of claim 11 wherein the non-reflective film of the two protective films of the polarizer is an optical correction film having an optical correction layer comprising an optically anisotropic layer. The optically anisotropic layer is a layer having a negative birefringence, comprising a compound having a discotic structural unit, the disc plane of the discotic structural unit is inclined with respect to the surface protective film plane, the discotic structure An angle made by the disk plane of the unit and the surface protective film plane is a polarizing plate that changes in the depth direction of the optically anisotropic layer. An image display apparatus comprising the antireflective film described in claim 1 or the polarizing plate described in claim 11 as the outermost surface of the display. A transmissive, reflective or transflective type liquid crystal display device comprising a TN-, STN-, VA-, IPS- or OCB- type, comprising at least one polarizer as described in claim 11.

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